CN101287565A - Method for producing shape-anisotropic metal particulate, colored composition, photosensitive transfer material, black image-fitted substrate, color filter and liquid crystal display device - Google Patents

Abstract

Disclosed is a method for producing shape-anisotropic metal particles which is characterized by comprising a step wherein a metal compound is reduced in the presence of a polymer dispersing agent having a mercapto group in a molecule. Also disclosed is a colored composition which is obtained by having a solvent having an SP value of not more than 25.8 MPa<1/2> contain the metal particles produced by the above-described method.

Description

Substrate, colour filter and the liquid crystal display cells of the manufacture method of shape anisotropy metal particle, coloured composition, photosensitive transfer printing material, band black image

Technical field

The present invention relates to substrate, colour filter and the liquid crystal display cells of the manufacture method of shape anisotropy metal particle, the coloured composition that contains this shape anisotropy metal particle, photosensitive transfer printing material, band black image.

Background technology

Black material is widely used in the Wiring pattern, conductive paste, conducting film, black matrix light-blocking images such as (black matrix) etc. of next door, dielectric pattern, electrode (conductor circuit) pattern, the electronic unit of printer's ink liquid, inkjet ink, resist, anti-solder flux, plasma display panel (PDP) with coloured composition.Described light-blocking image, except the clathrate between the edge of the black at the peripheral position that comprises display unit such as being arranged on liquid crystal indicator, plasma display apparatus, electroluminescent (E L) display unit, cathode ray tube (CRT) display unit, red, blue, green pixel or the black part of striated, and outside the so-called black matrixes such as black pattern of the point-like used of thin film transistor (TFT) (TFT) shading or wire (below be also referred to as " BM "), also comprise various light-blocking images.

BM is used for improving the demonstration contrast, and in the situation of the liquid crystal indicator of the driven with active matrix mode of having used thin film transistor (TFT) (TFT), be used to prevent that the electric current that is produced by light from leaking the image quality decrease that causes, thereby need high light-proofness (in optical density OD more than 3).

On the other hand, though liquid crystal indicator is applied to TV in recent years, but transmitance is low with regard to TV, and use the high color purity colour filter to obtain high brightness, therefore has the trend that brightness backlight uprises, and, require BM to have high light-proofness in order to prevent the transparent of decrease of contrast or surrounding edge part.

In addition, be arranged on the room of sunshine incident for a long time because of TV, the deterioration that might have the TFT that sunshine causes, in addition, even the girdle sensation of image is arranged owing to the OD height from (1), be the contrast height, and (2) externally liquid crystal whiting and the angle that do not see is set out under the light, also require BM to have high light-proofness.

As with the formation method of metal films such as chromium as the BM of light shield layer, following method is for example arranged: make metallic film by vapour deposition method or sputtering method, painting photoresist on this metallic film, then use the photomask of pattern with the photoresist exposure imaging with having BM, afterwards the metallic film that exposes is carried out etching, form BM (for example, with reference to non-patent literature 1) by the resist layer on the stripping metal film at last.

Because this method is used metallic film, so even have the little advantage that also can obtain high shaded effect of thickness.But because this method need be called the vacuum film formation operation or the etching work procedure of vapour deposition method or sputtering method, the problem of existence is that cost can not be ignored the load of environment when uprising.In addition, owing to be metal film, its reflectivity height, and under strong extraneous light, have the low problem of the contrast of demonstration.At this point, can use the method for low reflective chrome film (by 2 layers of film that constitutes of crome metal and chromium oxide etc.), but undeniable to be that cost can become higher as above-mentioned metallic film.

In addition, as other BM formation method, also known have use to contain for example method of the photosensitive polymer combination of carbon black of light-proofness pigment.As this method, the for example known BM formation method that self-localization method is arranged, promptly after forming red (R), green (G) and blue (B) pixel on the transparency carrier, coating contains the photosensitive polymer combination of carbon black on this pixel, carry out overall exposing (for example, referring to Patent Document 1) from R, the G of transparency carrier, the non-formation face side of B pixel.

Though just there are the problem of thickness thickening in the said method and the manufacturing cost step-down of comparing based on the etching method of above-mentioned metal film if will obtain sufficient light-proofness.Overlap between BM and R, G, the B pixel as a result (section poor), it is bad that the flatness variation of colour filter and causing produces the unequal demonstration of cell gap inequality, color of liquid crystal display cells.

On the other hand, people have proposed the method for following making BM: form the photonasty resist layer that contains hydrophilic resin on transparency carrier, and expose across having the photomask of BM with pattern, develop and formation concavo-convex (relief) on transparency carrier, the aqueous solution of this transparency carrier with the metallic compound that becomes the catalyst that electroless plating covers is contacted, make metallic compound be contained in concavo-convex in and drying after, heat-treat, contact by making concavo-convex and electroless plating on the above-mentioned transparency carrier cover liquid then, be produced on its inside and be dispersed with the BM (for example, referring to Patent Document 2) of the metallic that the shading of particle diameter 0.01～0.05 μ m uses equably.As above-mentioned metallic, record nickel, cobalt, iron, copper, chromium, only be shown with nickel as concrete example.

But this method makes the loaded down with trivial details treatment process of water many, and the concavo-convex formation-electroless plating that promptly comprises the exposure imaging operation covers the giving of catalyst-heat treatment-electroless plating and covers etc.Therefore, can not extravagantly hope and make BM at low cost.

In addition, put down in writing the example that in the coloured composition of making black pattern, uses the magnetic filler in the following patent documentation 3, but these examples are the above thick films of 10 μ m, and near the concentration the unit thickness is low, can not make the high light-blocking image of shading performance at low cost with film.

On the other hand, in following patent documentation 4 and 5, put down in writing use by metal particle nano wire as the example of conductive material, but clean, find when concentrating these particles a lot of agglutinators, cause the unequal demonstration of color bad when making the flatness variation of colour filter, therefore can not use with coloured material as display unit.

Known in addition, though use contain the coloured composition of shape anisotropy metal particle make the method for black pattern be in coloured composition, use draw ratio be the metal particle more than 2 example (for example, refer to Patent Document 4), but when using this metal particle to make the black colour filter, it is uneven to produce demonstration, can not be ideally as black matrix base plate.

So-called demonstration is not following inequality: under the sliding situation of black matrix base plate air spots, and the orientation turmoil of liquid crystal and become and show uneven reason, thus observed to light inequality during to liquid crystal indicator input grey test signal.Apparent in view " the strip inequality " that be shown as strip may be thought of as following inequality, promptly, the inequality that the inequality of the uneven thickness that generates when forming photo-sensitive resin, exposure inequality, development treatment, heat treated unequal orientation control produce when forming with projection, and the inequality that is produced with the interaction between projection and the liquid crystal by orientation control when working as liquid crystal indicator, but its mechanism still be can not determine.

In addition, preparation method by the shape anisotropy metal particle that is connected the chain that a plurality of metal particles form is disclosed in patent documentation 5 and 6.It is the manufacture method of the metal particle of purpose that this patent is to make conductive material.The shape anisotropy metal particle of the chain of known patent document 5 or 6 records is in the optical material purposes of colour filter or liquid crystal indicator and so on, with particle clean, during enrichment, dispersion stabilization is low, produce a lot of agglutinators, flatness as colour filter is received damage, does not therefore have use value.In addition, in the method for patent documentation 6 records, can only under very rare condition, just can obtain connecting catenulate particle, therefore be unsuitable for making.In addition, resulting particle length is so long as monodispersed relatively, and then absorption band is divided into 2 significantly, so can predict and will present gay colours.But particle length is uneven in the method that patent documentation 6 is put down in writing, and therefore can obtain the absorption band of the wide region different with single particle, but be difficult to obtain having the particle of desired tone.As mentioned above, it is difficult preparing tone based on shape anisotropy and have the preparation of coloured composition that reaches the dispersion stabilization of practical value as display material.

And though these metal particles are scattered in water to the high solvent of the polarity of lower alcohol and so on, the preparation that is not scattered in the metal particle of the organic solvent that hangs down polarity is difficult with having aggegation.

[patent documentation 1] Japan Patent spy opens clear 62-9301 communique

No. 3318353 communique of [patent documentation 2] Japan special permission

[patent documentation 3] Japan Patent spy opens the 2001-13678 communique

[patent documentation 4] Japan Patent spy opens the 2005-17322 communique

[patent documentation 5] Japan Patent spy opens the 2001-279304 communique

[patent documentation 6] WO2003/068674 communique

[non-patent literature 1] upright altogether (strain) distribution " カ ラ one TFT liquid crystal デ イ ス プ レ イ (colored TFT LCD) " 218-220 page or leaf (on April 10th, 1997) of publishing

Summary of the invention

The present invention finishes in view of aforesaid problem points.That is,

The invention provides the manufacture method of the shape anisotropy metal particle that can make the high shape anisotropy metal particle of dispersion stabilization.

The present invention also provides and can obtain the painted coloured composition of high concentration with film, and coloured composition and the photosensitive transfer printing material that can make high light-blocking image of shading performance and environment excellence with low cost especially are provided.The present invention further provides substrate, colour filter and liquid crystal indicator with the high band light-blocking image of film shading performance.

That is, the present invention is characterized in that for (1) provides a kind of manufacture method of shape anisotropy metal particle, have the macromolecule dispersing agent that in molecule, has sulfydryl in the presence of carry out the reduction of metallic compound operation.

Be characterised in that in a preferred implementation (2) the described shape anisotropy metal particle of preceding method (1) is connected by a plurality of metal particles and forms, and have different tones according to the variation of the connection length of described a plurality of metal particles.

Be characterised in that in another preferred implementation (3) the described shape anisotropy metal particle of the method for aforementioned (1) or (2) is formed by the composite particles of metallic compound and metal.

Be characterised in that in another preferred implementation (4), in any method of aforementioned (1)～(3), have absorption maximum in the wavelength region may more than 2 of described shape anisotropy metal particle in the wavelength region may of ultraviolet light, visible light and near infrared light, and absorbing wavelength is changed by the connection length that changes metal particle.

Be characterised in that in another preferred implementation (5) in any method of described (1)～(4), described macromolecule dispersing agent has sulfydryl more than at least 2 at the end of strand.

In addition, (6) of the present invention provide a kind of coloured composition, it is characterized in that, by being 25.8MPa in the SP value ^1/2Contain the resulting metal particle of any manufacture method of with good grounds aforementioned (1)～(5) in the following solvent and form.

Another preferred implementation (7) is characterised in that described coloured composition (6) also contains pigment.

In addition, another preferred implementation (8) is characterised in that, the pigment of described embodiment (7) be selected from carbon black, titanium is black and graphite at least a.

In addition, the present invention (9) provides a kind of photosensitive transfer printing material, it is the photosensitive transfer printing material that is provided with the photonasty light shield layer on supporter at least, it is characterized in that, described photonasty light shield layer forms by each described coloured composition in aforementioned (6)～(8).

In addition, the present invention (10) provides a kind of substrate with light-blocking image, it is characterized in that, has to use the light-blocking image that each described coloured composition makes in aforementioned (6)～(8).

In addition, the present invention (11) provides a kind of substrate with light-blocking image, it is characterized in that, has the light-blocking image that the photosensitive transfer printing material that uses described (9) makes.

In addition, the present invention (12) provides a kind of colour filter, it is characterized in that, uses each described coloured composition in aforementioned (6)～(8).

Further, the present invention (13) provides a kind of liquid crystal indicator, it is characterized in that, uses each described coloured composition in aforementioned (6)～(8).

The present invention can provide the preparation method of the shape anisotropy metal particle that can make the high shape anisotropy metal particle of dispersion stabilization.

The present invention also provides and can obtain the painted coloured composition of high concentration with film, especially can make the coloured composition and the photosensitive transfer printing material of high light-blocking image of shading performance and environment excellence with low cost.The present invention further provides substrate, colour filter and liquid crystal indicator with the high band light-blocking image of film shading performance.

The specific embodiment

The manufacture method of shape anisotropy metal particle of the present invention is characterised in that, have the macromolecule dispersing agent that in molecule, has sulfydryl in the presence of carry out the reduction of metallic compound operation.

Below, at first to describing by the shape anisotropy metal particle of manufacture method manufacturing of the present invention.

The shape anisotropy metal particle

The shape anisotropy metal particle that the present invention relates to is that a plurality of metal particles connect catenulate particle, be in containing molecule, to have in the feed metal compound solution of macromolecule dispersing agent of sulfydryl, the particle that makes by the reduction of carrying out metallic compound.The size of a particle of these a plurality of metal particles is preferably 2nm～100nm, and the connection length of a plurality of metal particles is preferably 5nm～1000nm, more preferably 5nm～500nm.

And, can make the tone difference by the connection length that changes a plurality of metal particles.For example, present redness when 2～4 particles are connected, present indigo plant～green when 5～8 are connected.

The shape anisotropy metal particle that the present invention relates to, in the wave-length coverage more than 2 of the wave-length coverage of ultraviolet light, visible light and near infrared light, have absorption maximum, can absorbing wavelength be changed by the connection length that changes described a plurality of metal particles.Specifically, the particle that 4～6 particles are formed by connecting has absorption maximum near the 400nm and near the 600nm, but the particle that 6～8 particles are formed by connecting is had absorption maximum near the 400nm and near the 700nm.

Metal particle

The metal particle that uses among the present invention is had no particular limits, can use any metal particle.In the metal particle of the present invention, the metal that preferably contains the 4th cycle of for example periodic table of elements, the 5th cycle and the 6th cycle that are selected from long period formula periodic table (IUPAC1991) as principal component, in addition, preferably contain be selected from the 2nd family, the 8th family, the 9th family, the 10th family, the 11st family, the 12nd family, the 13rd family and the 14th family metal as principal component.

Comprise at least a in the alloy that is selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead or these metals as the dispersed metal particle preferred example of described metallic.These metals, among 300～800nm of the wave-length coverage of being utilized, the viewpoint with optical absorption peak that the surface plasma body resonant vibration by metallic causes considers it is suitable.Further the example of preferred metal comprises at least a of the alloy that is selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium or these metals, and preferred metal comprises at least a of the alloy that is selected from copper, silver, gold, platinum, tin or these metals.

In addition, the metal particle among the present invention also can be the composite particles of metallic compound and metal.

Metallic compound

Said among the present invention " metallic compound " is the compound of the element beyond aforesaid metal and the metal.

As the compound of metal and other element, oxide, sulfide, sulfate, carbonate of metal etc. are arranged.Wherein form the angle consideration of particulate easily, preferred especially sulfide from color harmony.Comprise that as the example of these metallic compounds cupric oxide (II), iron sulfide, silver sulfide, copper sulfide (II), titanium are black etc.From tone, form the viewpoint of particulate and stability, preferred especially silver sulfide easily.

Composite particles

The composite particles of said metallic compound and metal among the present invention is meant that metal and metallic compound combine and become the material of a particle.Shape to compound particle has no particular limits.For example can enumerate at the inner different particle of particle, two kinds of particles and unify the particle that forms etc. with surface composition.In addition, metallic compound and metal can be separately a kind of also can be more than two kinds.Comprise the composite particles of the composite particles, silver of silver and silver sulfide and tin, the composite particles of silver-colored and cupric oxide (II) etc. as the object lesson of the composite particles of metallic compound and metal.

In the manufacture method of metal particle solution of the present invention, at first prepare to contain the feed metal compound solution of the macromolecule dispersing agent that in molecule, has sulfydryl.

Above-mentioned metallic compound just has no particular limits so long as can be dissolved in employed solvent.The example of above-mentioned metallic compound comprises the sulfate that is selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, plumbous one or more metals, acetate, nitrate, perchlorate, hydrochloride etc.Wherein, preferred acetate, nitrate, sulfate.

The example of above-mentioned solvent comprises water, organic solvent etc.

Above-mentioned organic solvent is had no particular limits, and the example of above-mentioned organic solvent comprises ketones such as acetone, alcohols such as methoxypropanol, ethoxy ethanol, propyl alcohol, 1-acetoxyl group-1-methoxy propane, diethylaminoethanol, ethylene glycol etc.When making water flushing precipitation, preferably use water-soluble solvent as post processing.The example of this water-soluble solvent comprises acetone, methoxypropanol, ethoxy ethanol, diethylaminoethanol etc.In addition, solvent is not limited to a kind, also a plurality of mixing can be used.

Preferably has amine-containing compound in the above-mentioned solvent.The example of this amine-containing compound comprises alkanolamines such as diethylaminoethanol, monoethanolamine, Propanolamine, triethanolamine, dimethylamino propyl alcohol, propylamine, butylamine, two trimethylene amine (dipropylene amine), 1, aliphatic amines such as 2-ethylenediamine, triethylene five amine, lipoid ring type amine such as piperidines, pyrrolidines, N-crassitude, morpholine, aromatic amines such as aniline, methylphenylamine, toluidines, anisidine, ethoxy aniline, the aralkylamine of benzylamine, benzene dimethylamine, N-methylbenzylamine and so on etc.

As the preferred alkanolamine of above-mentioned amine, preferred alcohol amine, Propanolamine, diethylaminoethanol etc., more preferably monoethanolamine.

Do not contain under the situation of above-mentioned amine-containing compound, preferably add base the pH of solution is remained on more than 8.

The manufacture method of shape anisotropy metal particle

As previously discussed, the manufacture method of shape anisotropy metal particle of the present invention is included under the existence of the macromolecule dispersing agent that has sulfydryl in the molecule, carries out the operation of the reduction of metallic compound.To describe macromolecule dispersing agent below.

Macromolecule dispersing agent

Above-mentioned macromolecule dispersing agent has the structure of introducing the high sulfydryl of the affinity of metal surface in high molecular weight polymers.

Think that above-mentioned macromolecule dispersing agent has been following effect: make generation through the metallic colloid particle of the reduction of metallic compound, and generate after decentralized stabilization in solvent.

The number-average molecular weight of above-mentioned macromolecule dispersing agent is preferably 600～500000.Insufficient less than 600 o'clock dispersion stabilizations, surpass the too high and operating difficulties sometimes of 500000 o'clock viscosity.More preferably 1000～300000, more preferably 3000～100000.

As operable macromolecule dispersing agent among the present invention, the macromolecular compound of for example preferred following general formula (1) expression.

General formula (1)

In the general formula (1), R ¹The linking group of expression singly-bound or 2 to 10 valencys that constitute by non-metallic atom, m, n represent 1 to 9, p represents macromolecular scaffold.

In the general formula (1), R ¹The linking group of expression singly-bound or 2 to 10 valencys that constitute by non-metallic atom.More particularly, R ¹At least a kind the atomic group of serving as reasons in the carbon atom that contains 1 to 100,0 to 10 nitrogen-atoms, 0 to 50 oxygen atom, 1 to 200 hydrogen atom and 0 to 20 's the sulphur atom constitutes.The example of linking group comprises the group that makes up following structural units and constitute more specifically.

The linking group of these multivalence has under the substituent situation; this substituent example comprises methyl; carbon numbers such as ethyl are 1 to 20 alkyl; phenyl; carbon numbers such as naphthyl are 6 to 16 aryl; hydroxyl; carboxyl; sulfamoyl; the N-sulfamoyl; carbon numbers such as acetoxyl group are 1 to 6 acyloxy; methoxyl group; carbon numbers such as ethyoxyl are 1 to 6 alkoxyl; chlorine; the halogen atom of bromine and so on; methoxycarbonyl; ethoxy carbonyl; the carbon number of cyclohexyl oxygen base carbonyl and so on is 2 to 7 alkoxy carbonyl; cyano group, the carbonate group of carbonic acid tert-butyl ester and so on etc.

In the general formula (1), there is no particular limitation to macromolecular scaffold that P represents.The preferred example of this macromolecular scaffold comprises the skeleton in (being total to) polymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, type siloxane polymer and their modifier and the copolymer that is selected from vinyl monomer.The more preferably example of this macromolecular scaffold comprises the skeleton in (being total to) polymer, esters polymer, ether polymer and their modifier and the copolymer that is selected from vinyl monomer.

In addition, from the angle of the dispersiveness of metal particle and/or fine particle composition, this macromolecular scaffold preferably dissolves in the solvent.

In addition, the preference of operable macromolecule dispersing agent also comprises the macromolecular compound that following general formula (2) is represented among the present invention.

General formula (2)

In the general formula (2), R ²Organic linking group of expression singly-bound or 2 to 10 valencys that constitute by non-metallic atom, R ³Organic linking group of expression singly-bound or the divalent that constitutes by non-metallic atom, m, n represent 1 to 9 integer, p represents macromolecular scaffold.

In the general formula (2), R ²Organic linking group of expression singly-bound or 2 to 10 valencys that constitute by non-metallic atom.More particularly, R ²At least a kind the atomic group of serving as reasons in the carbon atom that contains 1 to 60,0 to 10 nitrogen-atoms, 0 to 50 oxygen atom, 1 to 100 hydrogen atom and 0 to 20 's the sulphur atom constitutes.

With R ²The concrete example and the above-mentioned R of " organic linking groups of 2 to 10 valencys that constitute by non-metallic atom " of expression ¹In situation identical, comprise the combination of above-mentioned same structural units or this structural units and the group that constitutes.

Wherein, R ²The preferred concrete example of shown organic linking group is as follows, but the invention is not restricted to this.

Above R ²In the example of represented linking group, from synthetic easiness, with the group of the preferred especially dotted line of dissolubility equal angles of all kinds of solvents.

In the general formula (2), R ³Organic linking group of expression singly-bound or the divalent that constitutes by non-metallic atom, R ³Preference comprise the alkylidene that can have substituent straight chain, side chain or ring-type, arlydene, inferior heteroaryl, inferior aralkyl and-S-,-C (=O)-,-N (R ⁴)-,-SO-,-SO ₂-,-CO ₂-,-N (R ⁴) SO ₂-or the group of divalent that these groups are made up more than 2.Wherein, R ⁴Example comprise hydrogen atom or alkyl.The example of alkyl comprises that carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group are 1～4 alkyl.

In the general formula (2), P is identical with P meaning in the general formula (1), and preferred example is also identical.

Above macromolecule dispersing agent is the macromolecular compound with 1 above sulfydryl.This macromolecular compound can be synthetic by following any means.

1. the functional group of the polymer ends that will introduce in advance is transformed to the method for sulfydryl.

2. the method for Japanese patent laid-open 9-3108 record promptly, is carried out radical polymerization in the presence of thiocarboxylic acid, is hydrolyzed the synthetic polymer that has 1 sulfydryl endways after introducing carbothioic acid ester endways.

3. in the presence of free-radical generating agent, make the compound and the end that have 2 above sulfydryls in a part have the method for the polymer reaction of carbon-to-carbon double bond.

In these methods, because of can easily a plurality of functional groups being introduced polymer ends, so preferred 3 method.

Then, the macromolecule dispersing agent that has 2 above sulfydryls in 1 molecule is described.The example of the macromolecular compound that can use in this macromolecule dispersing agent comprises, has the compound of the arbitrary structures of the heterocycle that a plurality ofly is selected from aliphatic mercaptan, aromatic mercaptans, has sulfydryl in the molecule.

The concrete example of this macromolecule dispersing agent comprises 1, the 2-dithioglycol, 1, the 3-dimercaptopropane, 1, the 4-succinimide mercaptans, 2, the 3-succinimide mercaptans, 1, the 5-pentane disulfide thioalcohol, 1, the 6-ethanthiol, 1, hot two mercaptan of 8-, 1,9-mercaptan in the ninth of the ten Heavenly Stems two, 2,3-dimercapto-1-propyl alcohol, dithioerythritol, 2, the 3-dimercaptosuccinic acid, 1, the 2-dimercaptobenzene, 1, the 2-benzene dimethanethiol, 1, the 3-dimercaptobenzene, 1, the 3-benzene dimethanethiol, 1, the 4-benzene dimethanethiol, 3, the 4-dimercapto toluene, 4-chloro-1, the 3-dimercaptobenzene, 2,4,6-trimethyl-1, the 3-benzene dimethanethiol, 4,4 '-phenyl disulfide phenol, 2-hexyl amino-4,6-dimercapto-1,3, the 5-triazine, 2-lignocaine-4,6-dimercapto-1,3, the 5-triazine, 2-cyclohexyl amino-4,6-dimercapto-1,3,5-triazines, 2-di-n-butyl amino-4,6-dimercapto-1,3, the 5-triazine, ethylene glycol bis (3-mercaptopropionic acid ester), the two mercaptoacetates of butanediol, the ethylene glycol bis mercaptoacetate, 2,5-dimercapto-1,3,4-sulphur diazole, 2,2 '-(ethylene sulphur) diethyl mercaptan, 2,2 '-two (2-hydroxyls-3-sulfydryl propoxyl group phenyl-propane) etc. has the compound of 2 sulfydryls, 1,2,6-hexanetriol tri-thiol acetic acid esters, 1,3, the acid of 5-trithio cyanogen urea, 2,4,6-tri-thiol-1,3, the 5-triazine, trimethylolpropane tris (3-mercaptopropionic acid ester), trimethylolpropane tris mercaptoacetate etc. has the compound of 3 sulfydryls, pentaerythrite four (3-mercaptopropionic acid ester), pentaerythrite four mercaptoacetates, dipentaerythritol six (3-mercaptopropionic acid ester), dipentaerythritol six mercaptoacetates etc. have the compound of 4 above sulfydryls.

With respect to the total amount of metal quality that is contained in the feed metal compound solution and macromolecule dispersing agent quality, the amount of the macromolecule dispersing agent that is contained in the preferred above-mentioned raw materials metal compound solution is more than the 5 quality %.This macromolecule dispersing agent amount is during less than 5 quality %, and the dispersion stabilization in the time of might making reduction descends.This macromolecule dispersing agent amount there is not the special upper limit.

In the manufacture method of shape anisotropy metal particle of the present invention, comprise as the example of operation of the above-mentioned metallic compound of reduction and to add the reproducibility compound in the metal compound solution that contains above-mentioned macromolecule dispersing agent operation, and add metal compound solution in the reproducibility compound solution that contains above-mentioned macromolecule dispersing agent operation.From the angle of dispersion stabilization, preferably the former.And under the former situation, can use light such as ultraviolet ray to replace the reproducibility compound to reduce.

For above-mentioned the former operation, carry out following explanation.

In the solvent that is dissolved with above-mentioned metallic compound, add macromolecule dispersing agent and amine-containing compound, mix.In addition, above-mentioned metallic compound can be added to adding has in the solvent of macromolecule dispersing agent and amine-containing compound.

The concentration of metal in above-mentioned metal compound solution when reducing has no particular limits.Usually, preferably this metal concentration is more than the 10mmol/l.During less than 10mmol/l, the metal concentration of the colloidal metal solution that obtains is crossed low and inefficiency.From improving the angle of output, this metal concentration is preferably more than the 50mmol/l, more preferably more than the 140mmol/l.

After above-mentioned metal compound solution and macromolecule dispersing agent, amine-containing compound evenly mixed, add the reproducibility compound.Reduction reaction can be implemented in-20 ℃～300 ℃ temperature range, preferably in 0 ℃～100 ℃ temperature range.

Above-mentioned amine-containing compound can be used as reducing agent.At this moment, amine-containing compound is not mixed in before reduction reaction in the above-mentioned metal compound solution, but adds after with above-mentioned metal compound solution and macromolecule dispersing agent mixing.

In above-mentioned metal compound solution, it is more than 3% that above-mentioned amine is preferably by volume, more preferably more than 6%.

The example of operable above-mentioned reproducibility compound also comprises alkali metal borohydride salts, hydrazine compound, citric acid, tartaric acid, ascorbic acid, formic acid, formaldehyde, hydrosulfurous acid, sulfoxylate derivative, quinhydrones, hydroquinone derivatives, hydroxypropanone-s or the like such as sodium borohydride except amine.These can use separately or be used in combination with above-mentioned amine.

The preference of above-mentioned reproducibility compound comprises triethanolamine, ascorbic acid, quinhydrones, hydroquinone derivatives, hydroxypropanone-, wherein more preferably hydroxypropanone-.

The addition of above-mentioned reproducibility compound is preferably more than the needed amount of metallic reducing that will use in the above-mentioned metal compound solution of modulation.Less than this amount, then might reduce insufficient.In addition, this addition does not have the upper limit.

The latter's operation (metal compound solution being added in the reproducibility compound solution of pbz polymer dispersant) can be carried out based on above-mentioned the former operation.

In the present invention, obtain the shape anisotropy metal particle with state a plurality of, that connect catenulate spheroidal particle at random.The diameter of each this particulate is preferably 2～50nm, more preferably 5～30nm.The connection length of this particulate is preferably 5～1000nm, more preferably 5～500nm, more preferably 10～300nm.

The connection length of above-mentioned shape anisotropy metal particle is preferably even as far as possible.When monodispersity was high, this particulate can be used as the look material and preferably uses.

The connection length of above-mentioned shape anisotropy metal particle, minor axis length can change according to the number of the terminal sulfydryl of above-mentioned macromolecule dispersing agent, molecular weight etc.Under the identical situation of the kind of above-mentioned macromolecule dispersing agent, the connection length of above-mentioned shape anisotropy metal particle, minor axis length can change according to amount, feed metal compound concentrations, the concentration of amine, the amount of reproducibility compound, the temperature of macromolecule dispersing agent.

The metal concentration of the metal particle that the manufacture method by shape anisotropy metal particle of the present invention obtains is preferably more than the 80 quality %, more preferably 85 quality %, more preferably 90 quality %.

The solid formation branch concentration of the colloidal metal solution that obtains according to the manufacture method of shape anisotropy metal particle of the present invention has no particular limits, and for example can be 0.5～60 quality %.

The reducing agent of the salt that generates when the heteroions such as acetic acid ion that contain in the metal particle solution that makes according to the manufacture method of shape anisotropy metal particle of the present invention, reduction or these ions when containing amine, the base of using when not adding amine etc., excessive interpolation etc. from raw material, may negative effect be arranged to the stability of the metal particle solution that obtains, therefore preferably remove.The example of removing the method for these compositions comprises post-processing approach such as electrodialysis, centrifugation, ultrafiltration, decantation.Wherein, methods such as centrifugation, ultrafiltration, decantation, solvent extraction are owing to the metal concentration that makes metal particle solution simultaneously improves, and are therefore preferred.Decantation does not need special device, can easily carry out, and is therefore preferred.

By in the resulting metal particle solution of the manufacture method of shape anisotropy metal particle according to the present invention, add Weak solvent to above-mentioned macromolecule dispersing agent, metal particle easily forms big agglutination body in material solution.By this agglutination body being carried out decantation several times with Weak solvent, unwanted ion etc. can be removed, obtain the slurry of agglutination body.Afterwards,, be dissolvable in water again in the dispersion solvent, carry out decantation with the solvent that also can dissolve Weak solvent in order to remove the residual Weak solvent in the agglutination body slurry.By this operation, can obtain to be dissolved in again the metal particle agglutination body slurry in the dispersion solvent.

The solid formation branch of above-mentioned agglutination body slurry, preferably the weight with respect to this slurry is more than the 30 weight %, more preferably more than the 60 weight %, more preferably more than the 80 weight %.

For the Weak solvent of above-mentioned macromolecule dispersing agent, preferably make the solvent of above-mentioned impurity dissolving.

In above-mentioned metal particle solution, add the Weak solvent of above-mentioned macromolecule dispersing agent and after obtaining agglutination body, can take out agglutination body by suction filtration etc. rather than decantation.At this moment, impurity can be removed, and, the thickener that impurity obtains agglutination body can be removed with the solvent clean agglutination body of insoluble deagglomeration body.The aperture that is used for the filter membrane of above-mentioned suction filtration is preferably below the 100 μ m, more preferably below the 30 μ m.

Solid formation branch to the thickener of above-mentioned agglutination body has no particular limits, but the preferred weight of this thickener relatively is more than the 80 weight %.

By in the agglutination body of above-mentioned metal particle, adding the good solvent to macromolecule dispersing agent, the metal particle solution that can obtain disperseing.At this moment, disperse again, can stir, ultrasonic wave disperses, the pearl mill disperses etc. in order to make this agglutination body.

The preferred amphiphilic solvent such as acetone that uses in above-mentioned metal particle solution synthetic.In addition, preferred reducing agent and amine also are amphiphilic.In this case, from removing the ion equal angles, preferred water is as the Weak solvent to above-mentioned macromolecule dispersing agent, as being used for except that the preferred acetone of cleaning solvent that anhydrates, methyl alcohol, ethanol, propyl alcohol etc.

In order from the thickener of the agglutination body of above-mentioned metal particle, to remove the solvent that becomes impurity, can carry out drying to this thickener.

As dispersion solvent again, can be the solvent different kinds of liquid solvents that uses during with reduction to the good solvent of above-mentioned macromolecule dispersing agent.

On the other hand, can use above-mentioned centrifugation to replace above-mentioned decantation as subsidence style.At this moment, also preferably use solvent to carry out repeatedly cleaning so that impurity is removed.

By the metal particle solution that obtains through reduction feed metal compound under the existence of the macromolecule dispersing agent that has sulfydryl is endways carried out above-mentioned post processing, can obtain the solution that constitutes by the metal particle that macromolecule dispersing agent and a plurality of particle are formed by connecting.At this moment, measure the solid formation component that (TG-DTA) etc. obtains simultaneously from differential thermogravimetric amount, can be in the hope of the mass concentration of macromolecule dispersing agent and anisotropy metal particle.

Promptly connect the angle of length, particle diameter from the linking number of controlling the resulting metallic colloid particle that has connected, the manufacture method of shape anisotropy metal particle of the present invention is considered one of control method of particle diameter and shape of particle.

Shape anisotropy metal particle of the present invention can provide visibly different tone according to the difference of the connection length of particle, therefore can mix the look material that further obtains having different tones with any concentration by the particle that will have arbitrary hue.For example, can have the metal particle of red, blue, green tone, the preparation black pigment by mixing.

In the presence of the above-mentioned macromolecule dispersing agent of metal particle solution of the present invention by in molecule, having sulfydryl the reduction of feed metal compound is got, can add new macromolecule dispersing agent therein.Compare the metal concentration of the metal particle solution that obtains by previous methods, when having newly to add macromolecule dispersing agent the metal concentration of metal particle solution is significantly increased.Therefore, compared with the past, with this metal particle with reducing thickness significantly under the film forming situation of painted material.And, under the situation that this metal particle is used as conductive material, can make the heating condition of the electric conductivity when obtaining membranization more steady, therefore have the advantage that can be used in the low material of hear resistance.

Coloured composition

It is 25.8MPa that the metal particle that coloured composition of the present invention is obtained by the manufacture method that makes by anisotropy metal particle of the present invention is contained in the SP value ^1/2In the following solvent and form.That is, coloured composition of the present invention contains at least a shape anisotropy metal particle of having stated of the present invention.Coloured composition of the present invention can contain pigment particle, the polymer that becomes adhesive, photopolymerization monomer, Photoepolymerizationinitiater initiater, solvent etc. as required.

The SP value (solubility parameter) here is defined as the subduplicate numerical value of agglutinability metric density, expression molecular separating force.This SP value is can the quantification polymer or a kind of method for expressing of the polarity of low molecular compound such as solvent, can according to shown in following formula calculate, perhaps can survey and obtain.

SP value (δ)=(Δ Ev/V) ^1/2

In the following formula, Δ Ev represents that molar energy of vaporization, V represent molal volume.

In addition, as above-mentioned Δ Ev and V, can use the total (Δ Ev) and the molal volume (total vi) (V) of the mole vaporization heat (Δ ei) of the atomic group that " ROBERT F.FEDORS work " POLYMER ENGINEERING AND FEBRUARY " (Vol.14, No.2,151～153 pages, 1974) " put down in writing.

The SP value is 25.8MPa ^1/2The example of following solvent comprises methyl ethyl ketone, 1-propyl alcohol, propylene glycol monomethyl ether, acetone, cyclohexanone, N-methyl pyrrolidone, 2-propyl alcohol, and wherein preferred example comprises methyl ethyl ketone, 1-propyl alcohol, propylene glycol monomethyl ether, cyclohexanone.

Coloured composition of the present invention can be used for printer's ink liquid, inkjet ink, photomask and make material, printing are made next door with material, resist, anti-solder flux, plasma display panel (PDP), dielectric pattern, electrode (conductor circuit) pattern, electronic unit of waterproof Wiring pattern, conductive paste, conducting film, black matrix light-blocking images such as (black matrix) etc.

In order to improve the display characteristic that is used for colour filter and uses its employed colour filters such as display unit color liquid crystal display arrangement, and, can preferably use coloured composition of the present invention in order in extraneous light side of spacer portion, peripheral part and the TFT of colored pattern etc., light-blocking image to be set.

Coloured composition of the present invention can further be preferred at the edge of the black of the peripheral position setting of display unit such as liquid crystal indicator, plasma display display unit, EL display unit, CRT display unit, or the part of the black of clathrate between red, blue, the green pixel or strip.

Coloured composition of the present invention is preferably used as the black matrix of the point-like that is used for the TFT shading or black pattern of wire etc. especially.

Light-blocking image is made and is used coloured composition

Make the situation of using coloured composition to described coloured composition being particularly useful for light-blocking image, carry out following detailed description.

Use light-blocking image to make of coloured composition and form under the situation of light shield layer (layer before pattern forms), the optical density of the light shield layer of preferred per 1 micron thickness is more than 1.When making colour filter, when consideration prevents the fusion of metal particle in heating process, the content of shape anisotropy metal particle preferably is adjusted in the above-mentioned coloured composition, making the content of the shape anisotropy metal particle that contains in the formed light shield layer is 10～90 quality % with respect to the light shield layer gross weight, more preferably is adjusted into about 10～80 quality %.In addition, above-mentioned content is preferably the change of consideration by the caused optical density of average grain diameter of shape anisotropy metal particle.

In addition, the content with shape anisotropy metal particle in the photosensitive coloured composition described later also is identical.

Comprise black matrix (below, be called " BM ") in the scope of so-called among the present invention " light-blocking image ".So-called " BM " is meant the edge at the set black in the peripheral position of display unit such as liquid crystal indicator, plasma display display unit, EL display unit, CRT display unit, or the part of the black of clathrate between red, blue, green pixel or strip, further refer to point-like that the TFT shading is used or black pattern of wire etc.P.64, the definition of this BM is for example the wild safe flat work of villous themeda " liquid crystal デ イ ス プ レ イ System manufacturing apparatus Yong Language dictionary (the LCD manufacturing installation is used for dictionary) " the 2nd edition, Nikkan Kogyo Shimbun, 1996, put down in writing.As the example of light-shielding pattern, frontend panels (for example, the spy opens the 2003-51261 communique), the plasma that can enumerate OLED display (for example, the Japan Patent spy opens the 2004-103507 communique), PDP drive shading backlight in the liquid crystal (PALC) etc.

Because of improving, BM shows contrast, and in the situation of the liquid crystal indicator of the driven with active matrix mode of having used thin film transistor (TFT) (TFT), be used to prevent that the electric current that is produced by light from leaking the image quality decrease that causes, thereby need high light-proofness (OD counts more than 3 with optical density).

From the angle that sees through optical density (O.D.) of light shield layer, of the present invention to be used for the preferred minor axis length of shape anisotropy metal particle that light-blocking image makes of coloured composition be the silver-colored particulate of 4～100nm, more preferably the silver-colored particulate of 10～30nm.

Shape anisotropy metal particle among the present invention is preferably the state that is scattered here and there.The existence of the shape anisotropy metal particle during dispersion has no particular limits, but preferable shape anisotropy metal particle exists with stable dispersity, for example preferably exists with colloidal state.Under the situation of colloidal state, for example preferable shape anisotropy metal particle substantially disperses with the graininess of shape anisotropy.

Here, macromolecule dispersing agent used in the preparation of particulate solution can be further added, also different types of dispersant can be added with sulfydryl.The example of this different types of dispersant comprises the compound that contains mercapto, amino acid or derivatives thereof, peptide compounds, polysaccharide and from the natural polymer of polysaccharide, synthetic high polymer and from their gel etc.

The kind that contains the compound of mercapto used herein is had no particular limits, so long as have the compound of the mercapto more than 1 or 2, just can be arbitrarily.The example that contains the compound of mercapto (for example comprises the alkyl sulfide alcohols, methyl mercaptan, ethanethio etc.), the aryl mercaptan class (for example, thiophenol, thionaphthol, benzyl mercaptan etc.), the amino acid or derivatives thereof (for example, cysteine, glutathione etc.), peptide compounds (for example, the dipeptide compound that contains cysteine residues, tripeptide compound, the tetrapeptide compound, contain the oligopeptide compound of the amino acid residue more than five etc.), perhaps protein (for example, can be set forth in surface configuration metallothionein (metallothionein) is arranged, the globular protein of cysteine residues etc.) etc., still be not limited to these.Gelatin, polyvinyl alcohol, methylcellulose, hydroxypropyl cellulose, polyalkylene amine, polyacrylic part Arrcostab, PVP and PVP copolymer etc. as the polymer of the promising protecting colloid of high score subclass that is used for dispersant.For example on the books in " face material topical reference book (pigment dictionary) " (her rattan is levied the youth of department and compiles, and (strain) was towards the distribution of storehouse academy, 2000) about the polymer that can be used as dispersant.

In addition, in the dispersion liquid, also can suitably mix hydrophilic macromolecule, surfactant, anticorrisive agent or stabilizing agent etc.As hydrophilic macromolecule, so long as can be dissolved in water, and can under the low concentration state, keep the material of solution state in fact, just can use any material.The example of hydrophilic macromolecule comprises the material of protein such as gelatin, collagen, casein, fibronectin (fibronectin), laminine, elastin laminin and egg-derived white matter; Polysaccharides such as cellulose, starch, agarose, carrageenan, glucan, dextrin, chitin, chitosan, pectin, mannosan and the natural polymers such as material that are derived from polysaccharide; Synthetic high polymers such as polyvinyl alcohol, polyacrylamide, polyacrylic acid polyvinylpyrrolidone, polyethylene glycol, polystyrolsulfon acid, PAH; Perhaps be derived from these gel etc.When using gelatin, have no particular limits, comprise ox bone basic treatment gelatin, pigskin basic treatment gelatin, ox bone acid treatment gelatin, ox bone phthalandione processing gelatin, pigskin acid treatment gelatin etc. in its example for the kind of gelatin.

As above-mentioned surfactant, can use anion system, cation system, nonionic system, betaine is any in the surfactant, and special preferred anionic system and nonionic are surfactant.The hydrophile-lipophile balance of surfactant (HLB) value can not be that water system or organic solvent are to come without exception according to the solvent of coating fluid, preferred HLB was about surfactant of about 8～18 when but solvent was water system, and preferred HLB is about surfactant of about 3～6 under the situation of organic solvent system.

In addition, about above-mentioned HLB value, for example be recorded in " interfacial activity drug Ha Application ト Block Star Network (surfactant handbook) " (row during Jitian, advance that tree is good in rattan letter one, the mountain compiles, engineering books (strain) distribution clear and 62 years) in.Object lesson as above-mentioned surfactant has propylene glycol monostearate, PGML, diglycol stearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate etc.The example of surfactant is also recorded in above-mentioned " interfacial activity drug Ha Application ト Block Star Network (surfactant handbook) ".

Pigment

In the coloured composition of the present invention, can be by containing the black that pigment obtains netrual colour.

Pigment roughly is divided into organic pigment and inorganic pigment usually.The preferred organic pigment of the present invention.The example of the preferred pigment that uses comprises azo class pigment, phthalocyanine pigment, anthraquinone class pigment, dioxazines pigment, quinoline a word used for translation ketone pigment, isoindoline ketone pigment, nitropigments.The example of the preferred form and aspect of this organic pigment comprises yellow uitramarine, orange pigment, red pigment, violet pigment, blue pigment, viridine green, brown pigments, black pigment etc.

As light-blocking image make with and the preferred pigment that uses, have be selected from carbon black, titanium is black and graphite at least a.

The pigment that is used for photo-sensitive resin, classification is listed below according to form and aspect, but is not limited to these.

1) red pigment

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 123, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. pigment red 21 7, C.I. paratonere 220, C.I. paratonere 223, C.I. paratonere 224, C.I. paratonere 226, C.I. paratonere 227, C.I. paratonere 228, C.I. paratonere 240, C.I. pigment red 4 8:1, C.I. paratonere 209, C.I. pigment red 146, C.I. paratonere 11, C.I. pigment red 81, C.I. pigment red 123, C.I. pigment red 21 3, C.I. paratonere 272, C.I. paratonere 270, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 254, C.I.No.12085, C.I.No.12120, C.I.No.12140, organic pigments such as C.I.No.12315

2) viridine green

C.I. organic pigments such as pigment Green 7, C.I. pigment green 36, C.I.No.42053, C.I.No.42085, C.I.No.42095

3) blue pigment

C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 64, organic pigments such as C.I.No.42052, C.I.No.42090

4) yellow uitramarine

Pigment Yellow 12 (C.I.No.21090)

Example) Permanent Yellow DHG (trade name, Clariant Amada Co., Ltd. system), LionolYellow 1212B (trade name, Japan's China ink liquid are made Co., Ltd.'s system), IrgaliteR Yellow LCT (trade name, Ciba Co., Ltd. system), Symuler Fast Yellow (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment yellow 13 (C.I.No.21100)

Example) Permanent Yellow GR (trade name, Clariant Amada Co., Ltd. system), LionolYellow (trade name) 1313 (Japan's China ink liquid is made Co., Ltd.'s system)

Pigment Yellow 14 (C.I.No.21095)

Example) Permanent Yellow G (trade name, Clariant Amada Co., Ltd. system), LionolYellow 1401-G (trade name, Japan's China ink liquid are made Co., Ltd.'s system), Seika Fast Yellow 2270 (trade name, Dainichiseika Color Chem's system), Symuler Fast Yellow 4400 (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment yellow 17 (C.I.No.21105)

Example) Permanent Yellow GG02 (trade name, Clariant Amada Co., Ltd. system), SymulerFast Yellow 8GF (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment yellow 155

Example) Graphtol Yellow 3GP (trade name, Clariant Amada Co., Ltd. system)

Pigment yellow 180 (C.I.No.21290)

Example) Novoperm Yellow P-HG (trade name, Clariant Amada Co., Ltd. system), PV FastYellow HG (trade name, Clariant Amada Co., Ltd. system)

Pigment yellow 13 9 (C.I.No.56298)

Example) Novoperm Yellow M2R 70 (trade name, Clariant Amada Co., Ltd. system)

C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 17, C.I. pigment yellow 83, C.I. pigment yellow 86, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 117, C.I. pigment Yellow 12 5, C.I. pigment yellow 13 7, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 185, C.I. pigment yellow 147, C.I. pigment Yellow 14 8, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 185

5) magenta pigment

Paratonere 57:1 (C.I.No.15850:1)

Example) Graphtol Rubine L6B (trade name, Clariant Amada Co., Ltd. system), Lionol Red6B-4290G (trade name, Japan's China ink liquid are made Co., Ltd.'s system), IrgaliteR Rubine 4BL (trade name, Ciba Co., Ltd. system), Symuler Brilliant Carmine 6B-229 (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment red 122 (C.I.No.73915)

Example) Hosterperm Pink E (trade name, Clariant Amada Co., Ltd. system), LionolMagenta 5790 (trade name, Japan's China ink liquid are made Co., Ltd.'s system), Fastogen Super MagentaRH (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Paratonere 53:1 (C.I.No.15585:1)

Example) Permanent Lake Red LCY (trade name, Clariant Amada Co., Ltd. system), Symuler Lake Red C conc (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment red 4 8:1 (C.I.No.15865:1)

Example) Lionol Red 2B 3300 (trade name, Japan's China ink liquid are made Co., Ltd.'s system), SymulerRed NRY (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment red 4 8:2 (C.I.No.15865:2)

Example) Permenent Red W2T (trade name, Clariant Amada Co., Ltd. system), Lionol RedLX235 (trade name, Japan's China ink liquid are made Co., Ltd.'s system), Symuler Red 3012 (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment red 4 8:3 (C.I.No.15865:3)

Example) Permenent Red 3RL (trade name, Clariant Amada Co., Ltd. system), Symuler Red2BS (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Paratonere 177 (C.I.No.65300)

Example) CromophtalR Red A2B (trade name, Ciba Co., Ltd. system)

6) cyano group pigment

Pigment blue 15 (C.I.No.74160)

Example) Lionol Blue 7027 (trade name, Japan's China ink liquid are made Co., Ltd.'s system), FastogenBlue BB (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment blue 15: 1 (C.I.No.74160)

Example) Hosterperm Blue A2R (trade name, Clariant Amada Co., Ltd. system), FastogenBlue 5050 (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment blue 15: 2 (C.I.No.74160)

Example) Hosterperm Blue AFL (trade name, Clariant Amada Co., Ltd. system), IrgaliteRBlue BSP (trade name, Ciba Co., Ltd. system), Fastogen Blue GP (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment blue 15: 3 (C.I.No.74160)

Example) Hosterperm Blue B2G (trade name, Clariant Amada Co., Ltd. system), LionolBlue FG7330 (trade name, Japan's China ink liquid are made Co., Ltd.'s system), CromophtalR Blue4GNP (trade name, Ciba Co., Ltd. system), Fastogen Blue FGF (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment blue 15: 4 (C.I.No.74160)

Example) Hosterperm Blue BFL (trade name, Clariant Amada Co., Ltd. system), CyanineBlue 700-10FG (trade name, Japan's China ink liquid are made Co., Ltd.'s system), IrgaliteR Blue GLNF (trade name, Ciba Co., Ltd. system), Fastogen Blue FGS (Industrial Co., Ltd's system is learned in trade name, the China ink liquefaction of big Japan)

Pigment blue 15: 6 (C.I.No.74160)

Example) Lionol Blue ES (trade name, Japan's China ink liquid are made Co., Ltd.'s system)

Pigment blue 60 (C.I.No.69800)

Example) Hosterperm Blue RL01 (trade name, Clariant Amada Co., Ltd. system), LionogenBlue 6501 (trade name, Japan's China ink liquid are made Co., Ltd.'s system)

7) brown, black pigment

C.I. bistre 23, C.I. bistre 25, C.I. bistre 26, pigment black (carbon black C.I.No.77266) 7, TiO ₂, TiO, TiN or their mixtures, graphite

Example) the carbon black MA100 of Mitsubishi (trade name, Mitsubishi chemical Co., Ltd's system), the carbon black #5 of Mitsubishi (trade name, Mitsubishi chemical Co., Ltd's system), Black PearlsR 430 (trade name, Cabot Co.,Ltd's system), 12S and 12M (being trade name, Mitsubishi Materials commercial firm system)

8) orange pigment

C.I. pigment orange 36, C.I. pigment orange 43, C.I. pigment orange 51, C.I. pigment orange 55, C.I. pigment orange 59, C.I. pigment orange 61, C.I. pigment orange

9) violet pigment

C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 30, C.I. pigment violet 37, C.I. pigment violet 40, C.I. pigment violet 50

In addition, the example of the pigment that can use in the present invention comprise with reference to " the face material just list (pigment brief guide), Japanese pigment technology association compile, sincere Wen Tangxin light society, 1989 ", " COLOUR INDEX, THE SOCIETY OF DYES; COLOURIST, THIRD EDITION, 1987 " etc. the commodity that can suitably select.

Among the present invention, in the middle of the above-mentioned pigment, preferred phthalocyanine pigment, its example comprises that C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment yellow 83 etc. have the pigment of acidic-group.More preferred example comprises C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment yellow 83, C.I. pigment yellow 254, C.I. pigment yellow 36, C.I. pigment yellow 15, carbon black etc.

Pigment preferably uses and the form and aspect of the anisotropy metal particle pigment as complementary colours.In addition, pigment can use a kind of, also can be used in combination more than 2 kinds.The example of preferred pigment combinations comprises the combination of the pigment composition of complementary colours relation mutually that has of red colour system and the blue pigment composition with phase complementary colours relation that is and yellow system and violet, perhaps in said mixture, further add the combination of black pigment, the combination of the pigment of perhaps blue system, violet and black system.With respect to the gross weight of light shield layer, the scope of preferred 1～70 quality % of the content of the pigment of light shield layer, the more preferably scope of 1～40 quality %, the more preferably scope of 1～20 quality %.

Pigment is preferably made of disperseing equably in the coloured composition at light-blocking image.The average grain diameter of pigment is preferably below the 5 μ m, below the preferred especially 1 μ m.Colour filter is preferably below the 0.5 μ m with the average grain diameter of pigment.

The photonasty light-blocking image is made and is used coloured composition

Light-blocking image of the present invention is made preferably has photonasty with coloured composition.By adding photosensitive polymer combination, can make light-blocking image of the present invention and give photonasty with coloured composition.What comprise alkali-soluble binder polymer, Photoepolymerizationinitiater initiater in the scope of above-mentioned photosensitive polymer combination and have an ethene unsaturated double-bond passes through monomer (following be also referred to as sometimes " photopolymerization monomer ") that illumination injects capable addition polymerization etc.

But the composition that above-mentioned photosensitive polymer combination has composition that aqueous alkali develops and can develop with organic solvent.From the angle of the cost of security and developer solution, but the composition that preferred aqueous alkali develops.

Above-mentioned photosensitive polymer combination can be a partly solidified minus of accepting light or electron ray isoradial, also can be the partly solidified eurymeric of not accepting radioactive ray.

Comprise in the example of above-mentioned positive type photosensitive organic compound that using novolaks is the composition of resin.For example, can use the alkali-soluble novolac resin system of Japanese patent laid-open 7-43899 communique record.In addition, can use the positive-working photosensitive resin layer of Japanese patent laid-open 6-148888 communique record, promptly contain the alkali soluble resin of this communique record and as 1 of emulsion, the photo-sensitive resin of the mixture of the thermal curing agents of 2-naphthalene quinone di-azide sulfonic acid ester and the record of this communique.In addition, also can adopt the composition of Japanese patent laid-open 5-262850 communique record flexibly.

The photosensitive polymer combination that the negative light-sensitive resin combination example comprises the photoresist that is made of minus diazo resin and adhesive, optical polymerism composition, be made of azido cpd and adhesive, Chinese cassia tree acid type photosensitive polymer combination etc.Wherein particularly preferably be and contain Photoepolymerizationinitiater initiater, photopolymerization monomer and adhesive optical polymerism composition as basic constituent element.The example of this optical polymerism composition comprises " polymerizable compound B ", " polymerization initiator C ", " surfactant ", " gluing auxiliary agent " or other compositions of Japanese patent laid-open 11-133600 communique record.

For example, but the photosensitive polymer combination for negative light-sensitive resin combination and aqueous alkali development contains adhesive (the alkali-soluble adhesives of the thermoplastic resin of above-mentioned alkali-soluble etc.), Photoepolymerizationinitiater initiater with carboxyl and the monomer that contains the ethene unsaturated double-bond (following be also referred to as sometimes " photopolymerization monomer ") that can be injected capable addition polymerization by illumination as principal component.

The example of above-mentioned alkali-soluble adhesive comprises that side chain has the polymer of carboxyl.Its object lesson comprises that the Japan Patent spy opens clear 59-44615 communique, the special public clear 54-34327 communique of Japan Patent, the special public clear 58-12577 communique of Japan Patent, the special public clear 54-25957 communique of Japan Patent, the Japan Patent spy opens clear 59-53836 communique and Japan Patent spy and opens the methacrylic acid copolymer that clear 59-71048 communique is put down in writing etc., acrylic copolymer, itaconic acid copolymer, the crotonic acid copolymer, maleic acid, the maleic acid of partial esterification etc.And the example of above-mentioned alkali-soluble adhesive comprises that also side chain has carboxylic acid group's cellulose derivative.In addition, also preferred the use has adhesive behind the cyclic acid anhydride to the polymer addition with hydroxyl.Especially, (methyl) benzyl acrylate of putting down in writing in No. 4139391 specification of United States Patent (USP) is also contained in the example of above-mentioned alkali-soluble adhesive with the multiple copolymer of (methyl) acrylic acid copolymer or (methyl) benzyl acrylate and (methyl) acrylic acid and other monomers.

Above-mentioned alkali-soluble binder polymer, the polymer of the weight average molecular weight of the preferred acid number of selecting to use scope and 1000～300000 scope with 30～400mgKOH/g.Except above,, also can in not influencing the scope of development etc., add the alkali insoluble polymer in order to improve various performances for example for improve solidifying film strength.The example of the binder polymer of this alkali-soluble comprises pure soluble nylon or epoxy resin.

Whole solid formation with respect to photosensitive polymer combination divided, and the content of above-mentioned alkali-soluble binder polymer is preferably the scope of 10～95 quality % usually, more preferably the scope of 20～90 quality %.In the scope of 10～95 quality %, the cementability of photo-sensitive resin can be not too high, and the intensity and the photo sensitivity of formed layer can variation.

The example of above-mentioned Photoepolymerizationinitiater initiater comprises disclosed PVC シ Na Le Port リ ケ Le De ニ Le compound in No. 2367660 specification of United States Patent (USP), disclosed acyloin ether compound in No. 2448828 specification of United States Patent (USP), the disclosed aromatic series acyloin compound that is replaced by α-hydrocarbon in No. 2722512 specification of United States Patent (USP), the multinuclear naphtoquinone compounds of putting down in writing in each specification that No. the 2951758th, No. the 3046127th, United States Patent (USP) and United States Patent (USP), the combination of disclosed triarylimidazoles dimer and p-amino ketones in No. 3549367 specification of United States Patent (USP), benzothiazole compound and the trihalomethyl-s-triaizine compounds put down in writing in the special public clear 51-48516 communique of Japan Patent, trihalomethyl-s-triaizine compounds of putting down in writing in No. 4239850 specification of United States Patent (USP), the San halogen Jia oxadiazole compound of putting down in writing in No. 4212976 specification of United States Patent (USP) etc.More preferred example comprises trihalomethyl-s-triazine, San halogen Jia oxadiazole, triarylimidazoles dimer.

In addition, other spy opens " the polymerization initiator C " that put down in writing in the flat 11-133600 communique and is also included within the preferred example.

These Photoepolymerizationinitiater initiaters or Photoepolymerizationinitiater initiater class may be used alone, two or more kinds may be mixed to use, and especially preferably use more than two kinds.In addition, divide with respect to whole solid formation of photosensitive polymer combination, the content of Photoepolymerizationinitiater initiater is generally 0.5～20 quality %, is preferably 1～15 quality %.

The exposure sensitivity height, example painted, Photoepolymerizationinitiater initiater that display characteristic is good such as jaundice comprises the combination of diazoles Photoepolymerizationinitiater initiater and triazines Photoepolymerizationinitiater initiater.Wherein, 2-trichloromethyl 5-(to the styrene methyl)-1,3,4-oxadiazole and 2, two (the trichloromethyl)-6-[4-(N, N-di ethoxy carbonyl methyl) of 4--3-bromophenyl]-the s-triazine be combined as best.

The ratio of these Photoepolymerizationinitiater initiaters in the mass ratio of diazoles/triazines, is preferably 95/5 to 20/80, more preferably 90/10～30/70, most preferably be 80/20～60/40.

These Photoepolymerizationinitiater initiaters are on the books in Japanese patent laid-open 1-152449 communique, Japanese patent laid-open 1-254918 communique, Japanese patent laid-open 2-153353 communique.

Preferred example also comprises benzophenone.

It is near 15 to the 25 quality % time that light-blocking image is made with the shared ratio of pigment in the whole solid formation of coloured composition minute, by mix coumarin kind compound in above-mentioned Photoepolymerizationinitiater initiater, also can obtain identical effect.As coumarin kind compound, most preferably be 7-[2-[4-(3-methylol 1-piperidyl)-6-lignocaine] triazine radical amido]-3-phenyl cumarin.

The ratio of these Photoepolymerizationinitiater initiaters and coumarin kind compound in the mass ratio of Photoepolymerizationinitiater initiater/coumarin kind compound, is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30, most preferably be 40/60 to 60/40.

Wherein, the Photoepolymerizationinitiater initiater that can use in the present invention is not limited to these, can suitably select from known material.

Above-mentioned Photoepolymerizationinitiater initiater divides with respect to whole solid formation of photosensitive polymer combination, is generally 0.5～20 quality %, is preferably 1～15 quality %.Above-mentioned content can prevent the decline of photo sensitivity or image intensity in above-mentioned scope the time, can substantially improve performance.

The example of above-mentioned photopolymerization monomer comprises that boiling point is the compound more than 100 ℃ under normal pressure.Object lesson comprises polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, and simple function (methyl) acrylate such as phenoxy group ethyl (methyl) acrylate; Polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate, trimethylolpropane or glycerine etc. make after oxirane or epoxy third addition reaction multifunctional (methyl) acrylate of material of (methyl) acroleic acid esterification etc. again in the polyfunctional alcohol.

The further example of above-mentioned photopolymerization monomer comprises Japan Patent special public clear 48-41708 number, special public clear 50-6034 number of Japan Patent, the Japan Patent spy opens disclosed urethane acrylate (urethane acrylate) class in each communique of clear 51-37193 number, the Japan Patent spy opens clear 48-64183 number, special public clear 49-43191 number of Japan Patent, disclosed polyester acrylate class in each communique that Japan Patent is special public clear 52-30490 number is as the polyfunctional acrylic ester or the methacrylates such as epoxy acrylate class of epoxy resin and (methyl) acrylic acid reaction product.Wherein preferred example comprises trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate.Above-mentioned photopolymerization monomer can use separately, also can mix more than 2 kinds and use.Above-mentioned photopolymerization monomer is generally 5～50 quality % with respect to the whole solid content that divides that forms of photosensitive polymer combination, is preferably 10～40 quality %.Above-mentioned content is in above-mentioned scope the time, and the intensity of photo sensitivity and image does not descend, and the cementability of photonasty light shield layer can be superfluous.

Above-mentioned photosensitive polymer combination preferably also contains thermal polymerization and prevents agent except mentioned component.Above-mentioned thermal polymerization prevents that the example of agent from comprising quinhydrones, p methoxy phenol, p-tert-butyl catechol, 2,6-two-tert-butyl group-paracresol, betanaphthol, 1,2, aromatic hydroxy compounds such as 3-benzenetriol, benzoquinones, to the quinones of toluiquinone etc., the amine of naphthylamines, pyridine, para-totuidine, phenthazine etc., the aluminium salt of N-nitroso phenyl azanol or ammonium salt, chloranil, nitrobenzene, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc.

Can also add known additive as required in the above-mentioned photosensitive polymer combination, for example plasticizer, surfactant, adhesion promoter, dispersant, plasticizer, anti-agent, levelling agent, defoamer, fire retardant, polishing material, the solvent etc. of dropping down.

The example of above-mentioned adhesion promoter comprises alkyl phenol/formaldehyde phenolic resin varnish, polyethylene ethylether, PVI polyvinyl isobutyl ether, polyvinyl butyral resin, polyisobutene, SB rubber, butyl rubber, vinyl chloride vinyl acetate copolymer, chlorinated rubber, crylic acid resin bonding agent, the fragrance same clan, aliphatic category or aliphatic category Petropols, silane coupling agent etc.

In addition, the shape anisotropy metal particle is used as silver colloid when disperseing thing among the present invention, needs to use the water system composition as above-mentioned photosensitive polymer combination.The example of this photosensitive polymer combination also comprises as " SPP-M20 " of Toyo Synthetic Industry Co., Ltd.'s system of commercially available product etc. except the composition of record in the paragraph [0015] to [0023] of Japanese patent laid-open 8-271727 communique.

The light-blocking image of the application of the invention is made of coloured composition (containing photosensitive material) and is formed black matrix, can make the high black matrix of film and optical density.

Light-blocking image is made and is used photosensitive transfer printing material

Among the present invention, use above-mentionedly to have photosensitive light-blocking image and make and make light-blocking image with coloured composition and make and use photosensitive transfer printing material, and can use it to make light-blocking images such as deceiving matrix.

Above-mentioned photosensitive transfer printing material above-mentionedly has photosensitive light-blocking image and makes the material that is formed with the photonasty light shield layer with coloured composition for using at least on supporter, as required thermoplastic resin, intermediate layer or protective layer etc. can be set.

The scope of preferred 0.2～2 μ m of the thickness of above-mentioned photonasty light shield layer, the scope of preferred especially 0.2～0.9 μ m.

Supporter

The example that is used for the supporter of transfer materials of the present invention comprises known supporters such as polyester, polystyrene.Wherein the PET of biaxial tension is being preferred aspect cost, hear resistance, the dimensional stability.The thickness of this supporter is preferably about 15～200 μ m, more preferably 30～150 μ m about.The thickness of above-mentioned supporter is in above-mentioned scope the time, and the tabular wrinkle of galvanized iron that produces because of heat in the time of can effectively suppressing the lamination operation is also favourable on cost.

And also can be arranged on the conductive layer of putting down in writing in the Japanese patent laid-open 11-149008 communique on the above-mentioned supporter as required.

Thermoplastic resin

The thermoplastic resin of alkali-soluble preferably is set between supporter and photonasty light shield layer or supporter and intermediate layer in addition.

Because above-mentioned thermoplastic resin with can absorb the end liner surface concavo-convex (also comprise by established image etc. cause concavo-convex etc.) mode work as padded coaming, therefore preferably having can be according to this concavo-convex character of being out of shape.

Be contained in the resin of alkali soluble thermoplastic resin bed, be preferably at least a in saponified, the vinyltoluene of saponified, the styrene that is selected from ethene and acrylate copolymer and (methyl) acrylate copolymer and saponified, poly-(methyl) acrylate of (methyl) acrylate copolymer and (methyl) acrylate copolymer of (methyl) butyl acrylate and vinylacetate etc. etc. saponified etc.And can use according to the material that dissolves in the alkaline aqueous solution in the organic polymer of " プ ラ ス チ Star Network performance just list (plastics performance brief guide " (Japan Plastics Industry Federation, all Japan plastics forming industrial combination can be write, the census of manufacturing can be issued, distribution on October 25 nineteen sixty-eight).In addition, in these thermoplastic resins, preferred softening point is the resin below 80 ℃.So-called in the present specification " (methyl) acrylic acid " is the general designation to acrylic acid and methacrylic acid, is suitable for too for its derivative.

The resin of preferable weight-average molecular weight (Tg=0～140 ℃) scope that is 50,000～500,000 in the resin that above-mentioned alkali soluble thermoplastic resin bed contains, the more preferably resin of weight average molecular weight (Tg=30～110 ℃) scope that is 60,000～200,000.The object lesson of this resin comprises Japan Patent special public clear 54-34327 number, special public clear 55-38961 number of Japan Patent, special public clear 58-12577 number of Japan Patent, special public clear 54-25957 number of Japan Patent, the Japan Patent spy opens clear 61-134756 number, special public clear 59-44615 number of Japan Patent, the Japan Patent spy opens clear 54-92723 number, the Japan Patent spy opens clear 54-99418 number, the Japan Patent spy opens clear 54-137085 number, the Japan Patent spy opens clear 57-20732 number, the Japan Patent spy opens clear 58-93046 number, the Japan Patent spy opens clear 59-97135 number, the Japan Patent spy opens clear 60-159743 number, the Japan Patent spy opens clear 60-247638 number, the Japan Patent spy opens clear 60-208748 number, the Japan Patent spy opens clear 60-214354 number, the Japan Patent spy opens clear 60-230135 number, the Japan Patent spy opens clear 60-258539 number, the Japan Patent spy opens clear 61-169829 number, the Japan Patent spy opens clear 61-213213 number, the Japan Patent spy opens clear 63-147159 number, the Japan Patent spy opens clear 63-213837 number, the Japan Patent spy opens clear 63-266448 number, the Japan Patent spy opens clear 64-55551 number, the Japan Patent spy opens clear 64-55550 number, Japanese patent laid-open 2-191955 number, Japanese patent laid-open 2-199403 number, Japanese patent laid-open 2-199404 number, Japanese patent laid-open 2-208602 number, resin in the alkaline soluble aqueous solution of putting down in writing in each communique specification that the special hope of Japan Patent is flat 4-39653 number.More preferred example comprises that the Japan Patent spy opens methacrylic acid/2-EHA/benzyl methacrylate/methylmethacrylate copolymer of putting down in writing in the clear 63-147159 specification.

In addition, the resin of preferable weight-average molecular weight (Tg=30～170 ℃) scope that is 3,000～30,000 in the above-mentioned various resins, the more preferably resin of weight average molecular weight (Tg=60～140 ℃) scope that is 4,000～20,000.Its preferred concrete example can select the resin put down in writing in the above-mentioned patent specification, particularly preferred object lesson to comprise special public styrene/(methyl) acrylic copolymer put down in writing in each communique of 55-38961 number, Japanese patent laid-open 5-241340 number of recruiting of Japan Patent.

In addition, in order to regulate the bonding force between thermoplastic resin and the supporter, can in above-mentioned thermoplastic resin, add various plasticizer, various polymer, supercooling material, adhere to modifying agent, surfactant or releasing agent etc.The object lesson of preferred plasticizer comprises polypropylene glycol, polyethylene glycol, dioctyl phthalate, dibutyl phthalate (DHP), dibutyl phthalate, phosphoric acid (front three phenyl ester), tricresyl phosphate biphenyl ester, phosphoric acid biphenyl diphenyl ester, polyethyleneglycol (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the addition reaction product of epoxy resin and polyethyleneglycol (methyl) acrylate, the addition reaction product of organic diisocyanate and polyethyleneglycol (methyl) acrylate, the addition reaction product of organic diisocyanate and polypropylene glycol list (methyl) acrylate, the polycondensation product of bisphenol-A and polyethyleneglycol (methyl) acrylate etc.The amount of the plasticizer in the above-mentioned thermoplastic resin is generally below the 200 quality % with respect to this thermoplastic resin, is preferably 20～100 quality %.In addition, the thickness of alkali soluble thermoplastic resin bed is preferably more than the 6 μ m.As long as the thickness of thermoplastic resin is more than the 6 μ m, then the concavo-convex of end liner surface can be absorbed fully.In addition, the upper limit of the thickness of alkali soluble thermoplastic resin bed is considered to be generally below about 100 μ m from development, suitable manufacturing aspect, is preferably below about 50 μ m.

Among the present invention, the solvent of the coating fluid that uses during as the formation thermoplastic resin, just can use as long as can dissolve the resin that constitutes this layer, the example of above-mentioned solvent comprises for example methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, normal propyl alcohol, isopropyl alcohol etc. with being not particularly limited.

The intermediate layer

Can between interim supporter and photonasty light shield layer, the intermediate layer be set in the photosensitive transfer printing material of the present invention.

As the resin that constitutes the intermediate layer, so long as alkali-solublely just be not particularly limited.The example of this resin comprises that polyvinyl alcohol resin, polyvinylpyrrolidone are that resin, cellulose-based resin, acrylamide resin, PEO are that resin, gelatin, vinethene are resin, polyamide and their copolymer.In addition, also can use as polyester, to make and have the resin that carboxyl or sulfonic monomer form with being insoluble to the resin copolymerization of alkali usually.

Polyvinyl alcohol preferably wherein.The saponification degree of polyvinyl alcohol is preferably more than 80%, and more preferably 83 to 98%.

The preferred mixing more than two kinds of resin that constitutes the intermediate layer uses, and especially preferably polyvinyl alcohol and polyvinylpyrrolidone mixed the back as the resin that constitutes above-mentioned intermediate layer.Both quality are than preferably polyethylene pyrrolidones/polyvinyl alcohol=1/99-75/25, more preferably in the scope of 10/90-50/50.Above-mentioned mass ratio is in above-mentioned scope the time, the Apparently in Good Order﹠ Condition in intermediate layer, and the adhesiveness between the photonasty light shield layer that is provided with on it is good, and can prevent block to cut off property decline and the decline of the sensitivity that causes.

Also can in above-mentioned intermediate layer, add additives such as surfactant as required.

The thickness in intermediate layer is preferably 0.1～5 μ m, more preferably 0.5～3 μ m.The thickness in intermediate layer can not make oxygen cut off property decline, and can prevent to prolong the time of removing the intermediate layer when developing in above-mentioned scope the time.

As the coating solvent in intermediate layer, just be not particularly limited so long as can dissolve above-mentioned resin, preferably make water.Also preferably water Combination organic solvent is sneaked into the mixed solvent that forms in the water.Preferred object lesson comprises the mixed solvent of water, water/methyl alcohol=90/10, the mixed solvent of water/methyl alcohol=70/30, the mixed solvent of water/methyl alcohol=55/45, the mixed solvent of water/ethanol=70/30, the mixed solvent of water/1-propyl alcohol=70/30, the mixed solvent of water/acetone=90/10, the mixed solvent (representing mass ratio in this ratio) of water/methyl ethyl ketone=95/5.

The making of photosensitive transfer printing material

Preferred transfer materials of the present invention can form by the following method: have photosensitive light-blocking image and make solution with coloured composition and for example use that coating machines such as spin coater, rotation coating machine (ホ ワ イ ラ one), roll coater, curtain formula coating machine, knife coating, line rod coating machine (ワ イ ヤ one バ one コ one ), extruder are coated with, dryings of the present invention on supporter.Also can being identically formed of alkali-soluble thermoplastic resin is set.

Photosensitive transfer printing material of the present invention is provided with the photonasty light shield layer because of using photosensitive as mentioned above light-blocking image of the present invention to make with coloured composition, therefore can make to be film and the high light shield layer of optical density.

The preparation method of light-blocking image

Light-blocking image of the present invention makes by the light shield layer patterning that will use above-mentioned coloured composition or photosensitive transfer printing material and form.The thickness of light shield layer is generally about 0.2～2.0 μ m, is preferably below the 0.9 μ m.Light shield layer of the present invention is the layer that metal particle and pigment particle are disperseed, even therefore as above also can bring into play sufficient optical density (more than 3.5) for film.

In addition, there is no particular limitation for the method for using light-blocking image making of the present invention with coloured composition making (carrying out patterning) light-blocking image.Below enumerate the example of the formation method of the pattern of deceiving matrix.

In the 1st method, at first will contain the shape anisotropy metal particle and have photosensitive light-blocking image of the present invention and make and be coated on the substrate, form the photonasty light shield layer that contains the shape anisotropy metal particle with coloured composition.Afterwards, remove the part except that removing the pattern that gets by exposure imaging in the light shield layer, carry out pattern and form, thereby obtain light-blocking image.In addition, also can be formed on the above-mentioned photonasty light shield layer as protective layer with above-mentioned intermediate layer with the layer of forming.At this moment, the coating of coating fluid preferably uses spin-coating method to carry out.

In the 2nd method, the light-blocking image making of the present invention that at first will contain metal particle and non-photosensitive is coated on the substrate with coloured composition, forms the light shield layer that contains metal particle.Afterwards, coating photonasty liquid against corrosion forms resist layer on this light shield layer.Then,, on light shield layer, form pattern according to of the non-pattern part dissolving of this pattern with light shield layer by exposing the resist layer exposure imaging after forming pattern on the resist layer.Remove resist layer at last, make light-blocking image.

In the 3rd method, form coating layer in the part except that pattern on the substrate in advance, coating thereon contains the light-blocking image making coloured composition of the present invention of shape anisotropy metal particle and non-photosensitive then, forms the light shield layer that contains the particulate layer.Then, remove the coating layer and the light shield layer on it that begin to form simultaneously, make light-blocking image.

Use above-mentioned photosensitive transfer printing material to make in the example of method of light-blocking image, on the transmitance substrate, above-mentioned photosensitive transfer printing material layer is disposed and lamination in the mode that contacts with the photonasty light shield layer of photosensitive transfer printing material.Then supporter is peeled off from the layered product of photosensitive transfer printing material and transmitance substrate, thereafter across the light-blocking image formation light-blocking image that develops behind the above-mentioned layer with photomask exposure.

The preparation method of this light-blocking image does not need to carry out loaded down with trivial details operation, is preparation method cheaply.

Auxiliary layer

So-called auxiliary layer among the present invention is the layer with any above function of the following stated, from the viewpoint of resistance to impact, resistance to chemical reagents, solvent resistance, preferably with the light-blocking image layer in abutting connection with setting.

1. the layer that forms at its interface in order to increase the adhesion between substrate and the resin bed of the present invention.

Between substrate and the resin bed of the present invention or the reflection that prevents this interface that is provided with between resin bed of the present invention and other resin bed of the present invention the layer.

For increase between reflection layer of the present invention and the reflection layer adhesion and its layout setting the layer.

4. the layer that is provided with in order to protect resin bed of the present invention.

5. form and the layer of setting for resin bed of the present invention being carried out pattern with photoetch method.

As the concrete layer example of structure of using auxiliary layer of the present invention, from substrate-side, can enumerate light-blocking image layer/auxiliary layer, auxiliary layer/light-blocking image layer/auxiliary layer etc., but be not particularly limited in these.

The auxiliary layer photosensitive polymer combination

Auxiliary layer is following and get with photosensitive polymer combination, promptly, except the record composition of photosensitive polymer combination, add dyestuff beyond pigment, black or the black beyond black or the black etc. as required again, polymerization prevents agent (forbidding agent), other surfactants etc.

When using described pigment, preferably be dispersed in the photosensitive composition, so particle diameter is preferably below the 0.1 μ m, below the preferred especially 0.08 μ m.

As pigment and the dyestuff beyond above-mentioned black or the black, can enumerate Victoria's pure blue B O (C.I.42595), alkali Huang (C.I.41000), the black HB (C.I.26150) of fat, the Monot relies special (モ ノ ラ イ ト) yellow GT (C.I. pigment Yellow 12), permanent yellow GR (C.I. pigment yellow 17), permanent yellow HR (C.I. pigment yellow 83), permanent fuchsin FBB (C.I. pigment red 146), the red ESB of mother Hao Siteba (ホ ス -バ-system) (C.I. pigment purple 19), permanent ruby red FBH (C.I. paratonere 11), enamel is thought special as (Off ア ス テ Le) pink B Si pula (ス プ ラ) (C.I. pigment red 81), Mo Nasitela is as (モ Na ス ト ラ Le) fast blue (C.I. pigment blue 15), the Monot relies special fast black B (C.I. pigment black 1) and carbon, C.I. Pigment Red 97, C.I. pigment red 122, C.I. pigment red 149, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 180, C.I. paratonere 192, C.I. pigment red 21 5, C.I. pigment Green 7, C.I. pigment blue 15: 1, C.I. pigment blue 15: 4, C.I. alizarol saphirol 22, C.I. pigment blue 60, C.I. alizarol saphirol 64, C.I. pigment Violet 23, C.I. pigment blue 15: 6, C.I. pigment yellow 13 9, C.I. paratonere 254, C.I. pigment green 36, C.I. pigment yellow 13 8 etc.

The photosensitive polymer combination that obtains like this is as coating fluid, and coating on substrate or interim supporter, drying form the photo-sensitive resin that contains anti-reflection layer, and the operation through thereafter forms light-blocking image of the present invention.

Colour filter

Colour filter of the present invention has the pixel group more than 2 that presents different color that is made of dyed layer on the transmitance substrate, each pixel that constitutes above-mentioned pixel group has the structure that is separated by black matrix mutually, and above-mentioned black matrix makes with coloured composition or photosensitive transfer printing material by using above-mentioned light-blocking image of the present invention to make.Above-mentioned pixel group can be 2, more than 3 or 4.For example use 3 form and aspect that red (R), green (G) and blue (B) are arranged 3 the time.Under the situation of 3 kinds of pixel groups of configuration red, green, blue, the configuration of preferred mosaic (mosaic) type, triangular form etc., under the situation of the pixel group of configuration more than 4 kinds, any configuration all can.

The example of above-mentioned transmitance substrate comprises that the surface has known glass plates such as the soda-lime glass plate of silica tunicle, low-expansion glass plate, non-alkali glass plate, quartz glass plate or plastic foil etc.

Also can be behind the pixel group that forms on the transmitance substrate more than 2 in the making of colour filter by conventional method, the above operation forms black matrix for another example, perhaps also can form black matrix at first, forms the pixel group more than 2 thereafter again.

Therefore colour filter of the present invention shows contrast height and flatness excellence because of having aforesaid black matrix.

Liquid crystal display cells

Light-blocking image of the present invention is made can preferably be used in liquid crystal display cells with coloured composition.As one of liquid crystal display cells, can enumerate at least one element and between a pair of substrate of transmitance, possess at least and colour filter, liquid crystal layer and LCD drive g device are arranged (example of this device comprises simple matrix type of drive and driven with active matrix mode).As above-mentioned colour filter, can use following colour filter: have aforesaid a plurality of pixel group, each pixel that constitutes above-mentioned pixel group is separated by black matrix of the present invention mutually.Above-mentioned colour filter flatness height, the cell gap inequality between colour filter and the substrate does not take place in the liquid crystal display cells that therefore has this colour filter, and it is bad that the unequal demonstration of color does not take place.

In addition, in other embodiments of above-mentioned liquid crystal display cells, at least one element has colour filter, liquid crystal layer and LCD drive g device at least between a pair of substrate of transmitance, above-mentioned LCD drive g device has active component (for example TFT), and is formed with between each active component and uses light-blocking image of the present invention to make of coloured composition or photosensitive transfer printing material to make black matrix.

The example that can be used in the liquid crystal of above-mentioned liquid crystal display cells comprises nematic crystal, cholesteric crystal, smectic crystal, ferroelectric liquid crystals.

The substrate of band light-blocking image

The substrate of band light-blocking image of the present invention is by carrying out patterning and make being made to operate as mentioned above with the formed light shield layer of coloured composition by light-blocking image on the transmitance substrate.

In addition, the substrate of above-mentioned band light-blocking image can be used for the making of colour filter.

The thickness of light-blocking image is preferably 0.2～2.0 μ m in the substrate of this band light-blocking image (black matrix base plate), is preferably 0.2～0.9 μ m especially.Light shield layer is dispersed with the shape anisotropy metal particle in the above-mentioned black matrix base plate, even therefore also have sufficient optical density for aforesaid film.

The substrate of band light-blocking image of the present invention especially can unrestrictedly be applicable in the purposes such as carried terminals such as TV, notebook computer, liquid crystal projection apparatus, game machine, portable phone, digital camera, vehicle mounted guidance.

Liquid crystal display cells, liquid crystal indicator

Liquid crystal display cells of the present invention uses the substrate of the band photomask of having stated of the present invention to constitute.The substrate of band photomask of the present invention, in detail, by the composition of having stated that contains particulate of the present invention, display unit with coloring film form with black liquid or use light screening material and photomask constitute, therefore follow the color sensation that is exposed to hot environment change little, form and aspect good and have high light intensity, can realize that the contrast height of display image, the image with superior display quality show.

Liquid crystal display cells so long as have the liquid crystal display cells of the substrate of band photomask of the present invention, just has no particular limits, and can further use the inscape of known liquid crystal display cells to constitute.For example have the transmitance substrate that filter substrate reaches and its subtend disposes, the liquid crystal layer that between these substrates, is provided with, and the LCD drive g device (comprising simple matrix type of drive and driven with active matrix mode) that drives the liquid crystal of liquid crystal layer, can use the colour filter of having stated of the present invention to constitute as filter substrate.

Liquid crystal display cells of the present invention uses liquid crystal display cells of the present invention to constitute.(fine particle-containing composition of the present invention, display unit form with coloring film and use black liquid liquid crystal display cells of the present invention in detail by the substrate that uses the band photomask of having stated of the present invention, perhaps light screening material) and constitute, therefore follow the color sensation that is exposed to hot environment change little, form and aspect good and have high light intensity, can realize that the contrast height of display image, the image with superior display quality show.

Liquid crystal indicator of the present invention can further use the inscape of known liquid crystal indicator to constitute so long as the device that uses liquid crystal display cells of the present invention to make just has no particular limits.

The liquid crystal indicator of colored TFT mode for example is described in " カ ラ one TFT liquid crystal デ イ ス プ レ イ (colored TFT LCD) (upright publication (strain) distribution in 1996 altogether) ".

Light-blocking image of the present invention goes for the liquid crystal indicator that is made of these known parts.For example on the books in " markets of ' 94 liquid crystal デ イ ス プ レ イ periphery material ケ ミ カ Le ズ city Games (' 94 liquid crystal display associated materials chemicals) (island Itou Kentaro (strain) CMC 1994 distribution ", " the brilliant Seki Even of 2003 liquid city Games Now shape と looks forward to (present state and perspectives of 2003 liquid crystal relevant markets) (last volume) (good lucky (strain) CHIMERA of Fuji of table always grind 2003 etc. distribution) in the future " about these members, as the kind of LCD, can enumerate STN, TN, VA, IPS, OCS and R-OCB etc.

Below be described more specifically the present invention with embodiment, but the present invention is not limited to these embodiment.

Embodiment

Coloured composition

Polymer S-1's is synthetic

Make 1.22 parts pentaerythrite four (3-mercaptopropionic acid ester) (PEMP) (Sakai Chemical Industry Co., Ltd.'s system), and the polymethyl methacrylate (trade name: AA-6, Toagosei Co., Ltd's system) of 30.0 parts terminal methyl group propylene acidylate be dissolved in 46.8 parts methyl ethyl ketone, flow down in 80 ℃ of heating at nitrogen.To wherein add 0.03 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) (trade name: V-65, Wako Pure Chemical Industries, Ltd.'s system), flow down in 80 ℃ of heating 2 hours at nitrogen again, add 78.1 parts of methyl ethyl ketones after being cooled to room temperature, obtain the 20% solution (weight average molecular weight 18000 of polymer S-1 shown below thus; Macromolecule dispersing agent of the present invention).

As the stock silver compound, add the 1.8g silver acetate in the 45ml acetone in reaction vessel and divide the above-mentioned polymer S-1 that counts 0.28g with solid formation, mix.Further add monoethanolamine 7.5ml, mix.

Wherein, add the hydroxypropanone-of 22.5ml, obtain presenting the silver-colored particulate solution of bright-coloured and dense green.In the colloidal solution that obtains, add entry here, make it form agglutination body, and, obtain the silver colloid thickener with its suction filtration, repeatedly after the washing.(the SP value: 19) it being adjusted into solid formation branch weight is 8 weight % to use methyl ethyl ketone.Confirm that by microscopic examination this silver particles is that particle diameter is that a plurality of particles of 10～20nm are formed by connecting.Shortwave side maximum absorption wavelength and long wave side maximum absorption wavelength, the solid branch concentration (86.6 quality %) that forms of silver of silver colloidal solution are shown in Table 1.The solid branch concentration that forms of silver is tried to achieve as previously mentioned.

Embodiment 2～6

The synthesis example of polymer S-2

Make 0.81 part pentaerythrite four (3-mercaptopropionic acid ester) (PEMP) polymethyl methacrylate (trade name: AA-6, Toagosei Co., Ltd's system) of the terminal methyl group propylene acidylate of (Sakai Chemical Industry Co., Ltd.'s system) and 30.0 parts be dissolved in 46.2 parts the methyl ethyl ketone, flow down heating in 80 ℃ at nitrogen.To wherein add 0.03 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) (trade name: V-65, Wako Pure Chemical Industries, Ltd.'s system), flow down in 80 ℃ at nitrogen again and heated 2 hours, add 77.0 parts of methyl ethyl ketones after being cooled to room temperature, obtain the 20% solution (weight average molecular weight 21000 of polymer S-2 shown below thus; Macromolecule dispersing agent of the present invention).

By changing shown in the table 1, other carry out similarly to Example 1 separately except use level, reaction temperature with raw material, obtain the silver-colored particulate solution of embodiment 2～6.Embodiment 1 similarly measures their the solid branch concentration that forms of average grain diameter, particle linking number, shortwave side maximum absorption wavelength and long wave side maximum absorption wavelength, silver, and it be the results are shown in the table 1.

Comparative example 1

The use level of raw material, reaction temperature separately by changing shown in the table 1, are used commercially available wetting dispersing agent (trade name: デ イ ス パ one ピ Star Network 161 ^R(society of Bi Kehua association system)) as beyond the macromolecule dispersing agent, other carry out similarly to Example 1, obtain the silver-colored particulate solution of comparative example 1.The solid branch concentration that forms of average grain diameter, particle linking number, shortwave side maximum absorption wavelength and long wave side maximum absorption wavelength, the silver of comparative example 1 is measured similarly to Example 1, it be the results are shown in the table 1.

Embodiment 7

Polymer S-3's is synthetic

With 6.58 parts pentaerythrites four (3-mercaptopropionic acid ester) (PEMP) the methoxy poly (ethylene glycol) #1000 methacrylate (trade name: NK ester M-230G, Xin Zhong village chemical industry Co., Ltd. system) of (Sakai Chemical Industry Co., Ltd.'s system) and 30.0 parts be dissolved in 54.9 parts methyl ethyl ketone, flow down heating in 80 ℃ at nitrogen.To wherein add 0.06 part 2,2 '-azo two (2, the 4-methyl pentane nitrile) (trade name: V-65, Wako Pure Chemical Industries, Ltd.'s system), flow down in 80 ℃ at nitrogen again and heated 2 hours, add 91.5 parts of methyl ethyl ketones after being cooled to room temperature, obtain the 20% solution (weight average molecular weight 2200 of polymer S-3 shown below thus; Macromolecule dispersing agent of the present invention).

The making of photosensitive material

The golden particle dispersion liquid that preparation connects

Preparation is with the solution of the sodium hydrate aqueous solution 150g mixing of distilled water 3000g and 1N.In this solution, add above-claimed cpd S-3, be stirred to dissolving fully.Add sodium borohydride 3.6g again, be stirred to dissolving.This solution is as C liquid.

Preparation is mixed with the solution of 74.8g tetrachloro (III) auric acid tetrahydrate in 189g distilled water, stirred 30 minutes.This solution is D solution.

At this, in the liquid temperature remains in 50 ℃, the C liquid that is stirred, add D liquid, prepare golden particle dispersion liquid.

By in the golden particulate solution of preparation, adding nitric acid pH is transferred to 4, make golden microparticle agglutination sedimentation.

Remove the top clarified solution of aggegation gold particulate liquid, with the agitator stirring aggegation after the golden microparticulate, was left standstill 1 hour, make the sedimentation of the aggegation Jenner grain of rice once more to wherein adding distilled water.Remove the top clarified solution, obtain aggegation gold particulate.In carrying out the resulting aggegation gold of this operation of several particulate repeatedly, add methyl ethyl ketone to making gold become 8 quality %, shone the ultrasonic wave 5 minutes of 20kHz with ultrasonic homogenizer (trade name: sonifierII type, than letter energy (branson) commercial firm system).Use afterwards ultrasonic homogenizer (trade name: model2000bdc-h 40:0.8 type, can commercial firm than letter system) ultrasonic wave 10 minutes of irradiation 40kHz.During the ultrasonic irradiation, with constant-temperature water circulating device (trade name: Network one Le ニ Network ス ^RCTW400, YAMATO science society system) cooling, make test portion liquid maintain 25 ℃.Golden particulate in the test portion liquid that obtains, arithmetic mean particle diameter are 45nm, the standard deviation that counts is 34nm.It is 87.3% that Jin Gu forms branch concentration.Jin Gu forms branch concentration and tries to achieve as previously mentioned.

The preparation of coating fluid of photonasty light shield layer

Mix following composition, preparation photonasty light shield layer coating fluid.

Form

Described golden particle dispersion liquid 100g

Methyl ethyl ketone 39g

Fluorine class surfactant 0.1g

(Industrial Co., Ltd's system is learned in trade name: F780F, the China ink liquefaction of big Japan)

Hydroquinone monomethyl ether 0.001g

Benzyl methacrylate/methacrylic acid copolymer 2.1g

(mol ratio=73/27, molecular weight 30000)

Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] carbamyl] phenyl] sebacate 0.1g

The preparation of protective layer used coating fluid

Mix following composition, prepare protective layer used coating fluid.

Polyvinyl alcohol 3.0g

(trade name: PVA205, Kuraray Co., Ltd. system)

Polyvinylpyrrolidone 1.3g

(trade name: PVP-K30, ISP Japan commercial firm system)

Distilled water 50.7g

Methyl alcohol 45.0g

The making of photosensitive material

On glass substrate, use spin coater be coated with above-mentioned photonasty light shield layer with coating fluid so that dry film thickness is 0.8 μ m, 100 ℃ of dryings 5 minutes, formation photonasty light shield layer.Then, use spin coater to be coated with above-mentioned protective layer used coating fluid thereon,, form protective layer, make photosensitive material 100 ℃ of dryings 5 minutes so that dry film thickness is 1.5 μ m.

The making of black matrix

With プ ロ キ シ ミ テ イ one type exposure machine (electronic engineering Co., Ltd. of Hitachi system) with extra-high-pressure mercury vapour lamp; under with substrate and the vertically upright state firmly of mask (having the quartzy exposed mask of picture pattern); it is 200 μ m that distance is set between exposed mask face and the protective layer, and with light exposure 70mJ/cm ²Carried out pattern exposure.Then, use development treatment liquid (trade name: TCD, photo film Co., Ltd. of Fuji system) to carry out development treatment (33 ℃, 20 seconds) as alkaline-based developer.Drawing is of a size of 10 inches, and pixel is 480 * 640, and in addition, the opening that obtains black matrix width and be 24 μ m, pixel portion is the black matrix of 86 * 304 μ m.

Estimate

Carry out following evaluation for the black matrix that obtains.The results are shown in the table 2.

The mensuration of optical concentration

Measure a little thickness of light of film according to following method.

At first, coating is arranged at the photonasty light shield layer of deceiving on the preceding glass substrate of matrix making, uses described extra-high-pressure mercury vapour lamp to carry out 500mJ/cm from the coated face side ²Exposure.Then, use Macbeth illuminometer (trade name: TD-904, Macbeth society system) to measure this optical density (O.D.).The optical density (OD0) that also uses the same method and measured glass substrate deducts OD0 from above-mentioned O.D., as the optical density of film.

The making of liquid crystal indicator

Use the substrate that is formed with black matrix that obtains in above-mentioned, utilize the method for record in first embodiment [0079]～[0082] in Japanese patent laid-open 11-242243 communique, make liquid crystal indicator, results verification do not have a demonstration that delays work.

Estimate

The liquid crystal indicator that obtains has been carried out following evaluation.Result such as table 1.

Uneven mensuration

During incident grey test signal, with the naked eye reach magnifying glass and observe in the liquid crystal indicator, judge to have or not uneven generation.Do not have fully uneven for A, can confirm a small amount of uneven for B, can significantly confirm the uneven X that is.

Embodiment 8

The preparation of the silver-colored particle dispersion liquid that connects

Make silver-colored particle dispersion liquid in the same manner with embodiment 2, and except the golden particle dispersion liquid that uses this silver particle dispersion liquid replacement embodiment 7, other and embodiment 7 make black matrix and the liquid crystal indicator of embodiment 8 in the same manner, carry out same evaluation result such as table 2.

Embodiment 9

The preparation of the silver-colored particle dispersion liquid that connects

As the feed metal compound solution, add 17g silver acetate, the described polymer S-3 of 3.0g, 60g monoethanolamine among the acetone 380g in being placed on reaction vessel, be stirred to silver acetate and dissolve fully.

Wherein, add the 160g hydroxypropanone-, obtain having the silver-colored particulate solution that has absorption in the high four corner that absorb, in the visual field at 400nm and 710nm place.Here the colloidal solution that obtains is dissolved in methyl ethyl ketone after repeatedly washing, and being modulated to solid formation branch weight is 8 weight %.By microscopic examination, confirmed should the silver particulate to be that a plurality of mean particle diameters are the material that the particle of 10nm is formed by connecting.The solid formation of silver branch concentration is 90.1 quality %.The solid branch concentration that forms of silver is tried to achieve as previously mentioned.

Except the silver-colored particle dispersion liquid that uses above-mentioned making replaces the golden particle dispersion liquid of embodiment 7, make black matrix and the liquid crystal indicator of embodiment 9 similarly to Example 7, carried out same evaluation, result such as table 2.

Embodiment 10

Make the silver-colored particulate that connects similarly to Example 8, in the acetone dispersion liquor of the silver-colored particulate of this 200g, add the polymer (copolymer of vinylpyrrolidone/vinyl acetate=60/40 (mass ratio), molecular weight 5000) of 0.95g, stirred 30 minutes.

When then stirring, the sodium sulfide solution that adds concentration 7.2 quality % is so that the sulfuration rate of metal is 10%.

Here so-called " sulfuration rate " is sulfureted ratio in the metal particle, and 0% expression of sulfuration rate does not have sulfureted state fully, and sulfuration rate 100% becomes the state of sulfide fully for all particles.Fluid temperature when adding sodium sulfide solution is 23 ℃.

After adding sodium sulfide solution, this state continues to stir 30 minutes down.

By above operation, make galactic nucleus shell particulate with silver sulfide shell.

The mass ratio of shell is 0.11 in the particle.This mass ratio is that the molal quantity of silver from particle and sulphur calculates and tries to achieve.Both molal quantitys by for spin coating on the PET supporter test portion of particle dispersion, use the x-ray fluorescence analysis of fluorescent x-ray analyzer (trade name: Type3370E), Co., Ltd. of science system) to try to achieve.When the molal quantity of sulphur and silver is respectively done for oneself ms, mA, the Ag of shell ₂The molal quantity of S is that the molal quantity of the Ag of ms, nuclear is mA-2ms.

It is as follows that thereby the mass ratio of shell and nuclear becomes:

(ms/247.8)∶(mA-2ms/107.9)。

With after silver/silver sulfide core-shell particles solution repeatedly washes of above-mentioned making, take out aggegation silver/silver sulfide core-shell particles by suction filtration, use methyl ethyl ketone to be adjusted into 8 quality %.The golden particulate in using this silver/silver sulfide core-shell particles solution replacement embodiment 7, other and embodiment 7 make black matrix and the liquid crystal indicator of embodiment 10 in the same manner, have carried out same evaluation, result such as table 2.

Embodiment 11

In embodiment 1, when preparation photonasty light shield layer is used the modulation of coating fluid, use the silver-colored particulate and the carbon black (trade name: CFP-FF-949K, Fujiphoto Electronics Materials Co., Ltd system) of embodiment 8 records to replace golden particle dispersion liquid, making the addition with respect to the carbon black of the addition of silver-colored microparticulate thing is silver-colored particulate: carbon black=95: 5 (mass ratio), in addition make black matrix and the liquid crystal indicator of embodiment 11 in the same manner with embodiment 7, carried out same evaluation, the result is as shown in table 2.

Comparative example 2

Preparation is mixed with 41g tetrachloro (III) auric acid tetrahydrate, the commercially available wetting dispersing agent (trade name: デ イ ス パ one ピ Star Network 161 of 10g in the 380g pure water ^R(Bi Kehua association society system)), the NaOH aqueous solution of 80g 1N.In this solution, add the 3g sodium borohydride, stir the golden particulate that obtained having high absorption band in 30 minutes at the 500nm place.After will obtaining colloidal solution here and concentrating through suction filtration, be dissolved in ethanol, being prepared into solid formation branch weight is 8 quality %.Form total solid that the solid formation of gold branch concentration proportion is 70.5 quality % in the branchs weight.Should the gold particle dispersion liquid have shone the ultrasonic wave 5 minutes of 20kHz with ultrasonic homogenizer (trade name: sonifierII type, can commercial firm's system) than letter.Use afterwards ultrasonic homogenizer (trade name: model2000bdc-h 40:0.8 type, can commercial firm than letter system) ultrasonic wave 10 minutes of irradiation 40kHz.During the ultrasonic irradiation, with constant-temperature water circulating device (trade name: Network one Le ニ Network ス ^RCTW400, YAMATO science commercial firm system) cooling, make test portion liquid maintain 25 ℃.The arithmetic mean particle diameter of the golden particulate in the test portion liquid that obtains is 42nm, the standard deviation that counts is 56nm.

Except use the golden particulate made in above-mentioned, with coating fluid form change into following, other and embodiment 7 make in the same manner and deceive matrix and liquid crystal indicator, have carried out same evaluation.The result is as shown in table 2 below.

Described golden particle dispersion liquid 100g

1-propyl alcohol 39g

Fluorine class surfactant 0.1g

(Industrial Co., Ltd's system is learned in trade name: F780F, the China ink liquefaction of big Japan)

Hydroquinone monomethyl ether 0.001g

Benzyl methacrylate/methacrylic acid copolymer 2.1g

(mol ratio=73/27, molecular weight 30000)

Two [4-[N-[4-(4, the two trichloromethyls of 6--s-triazine-2-yl) phenyl] carbamyl] phenyl] sebacate 0.1g

The preparation of protective layer used coating fluid

Mix following composition, prepare protective layer used coating fluid.

Polyvinyl alcohol 3.0g

(trade name: PVA205, Kuraray Co., Ltd. system)

Polyvinylpyrrolidone 1.3g

(trade name: PVP-K30, ISP Japan commercial firm system)

Distilled water 50.7g

Methyl alcohol 45.0g

Comparative example 3

As the feed metal compound solution, add the 6g silver acetate among the acetone 180g in being positioned over reaction vessel, stir.Further add the commercially available wetting dispersing agent (trade name: デ イ ス パ one ピ Star Network 161 of 3g ^R(Bi Kehua association society system)), the monoethanolamine of 25g, be stirred to silver acetate and dissolve fully.To wherein adding hydroxypropanone-50g, obtain presenting yellow silver-colored particulate solution.This particle has high the absorption at the 400nm place, its arithmetic mean particle diameter is 51nm, the standard deviation that counts is 63nm.

By electron microscope observation, find that this silver particulate is that average grain diameter is the spheroidal particle of 30nm.Through repeatedly the washing clean this silver particulate, make it be dissolved in methyl ethyl ketone again, make solid formation branch weight be 8 quality % be prepared.

Use the silver-colored particulate of above-mentioned making to replace the golden particulate of embodiment 7, prepare the black matrix and the liquid crystal indicator of comparative example 3 in the same manner, carry out same evaluation with embodiment 7.The result is as shown in table 2.

Comparative example 4

With length average out to 100nm, the width average out to 100nm of 73.5g, the dull and stereotyped silver-colored particulate of thickness average out to 46nm, the commercially available wetting dispersing agent (trade name: デ イ ス パ one ピ Star Network 161 of 1.05g ^R(society of Bi Kehua association system)) and methyl ethyl ketone 110.3 mixing, use ultrasonic dispersing machine (trade name: Ultrasonic generator model US-6000ccvp, nissei commercial firm system) to make its dispersion, obtain dull and stereotyped silver-colored particle dispersion liquid.

Use the silver-colored particle dispersion liquid of above-mentioned making to replace the golden particle dispersion liquid of embodiment 7, make the black matrix and the liquid crystal indicator of comparative example 4 in the same manner, carried out same evaluation with embodiment 7.Result such as following table 2.

Table 2

	Metal	Shape	And the pigment of usefulness	Optical density	Show uneven
						Embodiment 7	Gold	Connect catenulate particle	-	4.1	○
Embodiment 8	Silver	Connect catenulate particle	-	4.2	○
						Embodiment 9	Silver	Connect catenulate particle	-	4.5	○
Embodiment 10	Silver/silver sulfide	Connect catenulate particle	-	4.3	○
						Embodiment 11	Silver	Connect catenulate particle	Carbon black (5%)	4.1	○
Comparative example 1	Gold	Ball	-	1.2	○
						Comparative example 2	Silver	Ball	-	1.0	○
Comparative example 3	Silver	Dull and stereotyped	-	4.0	△

According to table 2, in embodiments of the invention 7～11, optical density high and do not observe fully show uneven.Comparatively speaking, in the uneven evaluation of the optical density of comparative example 2～4 and demonstration, can not be satisfied both results simultaneously.

The disclosed full content of Japanese publication 2005-305026 is quoted by this specification by reference.Whole documents, patent application and the technical standard put down in writing in this specification, with each document, patent application and technical standard specifically, the situation of record respectively comparably, by with reference to being introduced in this specification.

Utilizability on the industry

The invention provides the manufacture method of the shape anisotropy metal particle that can make the high shape anisotropy metal particle of dispersion stabilization. The present invention also provides and can obtain the painted coloured composition of high concentration with film, and especially providing can be with the high light-blocking image of low cost fabrication shading performance and coloured composition and the photosensitive transfer printing material of environment excellence. The present invention further provides with the high substrate with light-blocking image of the shading performance of film, colour filter and liquid crystal indicator.

Claims (19)

1. the manufacture method of a shape anisotropy metal particle is characterized in that, comprise,

In molecule, have sulfydryl macromolecule dispersing agent in the presence of, the operation of carrying out the reduction of metallic compound.

2. the manufacture method of shape anisotropy metal particle as claimed in claim 1 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.

3. the manufacture method of shape anisotropy metal particle as claimed in claim 1 is characterized in that,

Described shape anisotropy metal particle is formed by the composite particles of metallic compound and metal.

4. the manufacture method of shape anisotropy metal particle as claimed in claim 1 is characterized in that,

Have absorption maximum in the wavelength region may more than 2 of described shape anisotropy metal particle in the wavelength region may of ultraviolet light, visible light and near infrared light, and absorbing wavelength is changed by the connection length that changes metal particle.

5. the manufacture method of shape anisotropy metal particle as claimed in claim 1 is characterized in that,

Described macromolecule dispersing agent has sulfydryl more than at least 2 at the end of strand.

6. a coloured composition is characterized in that,

By being 25.8MPa in the SP value ^1/2Contain the shape anisotropy metal particle in the following solvent and form, and

Described metal particle is by comprising that following operation is that the manufacture method of feature makes, the operation of described operation for carrying out the reduction of metallic compound in the presence of the macromolecule dispersing agent that has sulfydryl in molecule.

7. coloured composition as claimed in claim 6 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.

8. coloured composition as claimed in claim 6 is characterized in that, also contains pigment.

9. coloured composition as claimed in claim 8 is characterized in that, described pigment is to be selected from least a in the black and graphite of carbon black, titanium.

10. photosensitive transfer printing material, it is to comprise supporter and the photosensitive transfer printing material of the photonasty light shield layer that contains coloured composition that is provided with on described supporter, it is characterized in that,

Described coloured composition is by being 25.8MPa in the SP value ^1/2Contain the shape anisotropy metal particle in the following solvent and form, and

Described metal particle is by comprising that following operation is that the manufacture method of feature makes, the operation of described operation for carrying out the reduction of metallic compound in the presence of the macromolecule dispersing agent that has sulfydryl in molecule.

11. photosensitive transfer printing material as claimed in claim 10 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.

12. the substrate with light-blocking image, it is the substrate that comprises the band light-blocking image of the light-blocking image that contains coloured composition, it is characterized in that,

Described coloured composition is by being 25.8MPa in the SP value ^1/2Contain the shape anisotropy metal particle in the following solvent and form, and

Described metal particle is by comprising that following operation is that the manufacture method of feature makes, the operation of described operation for carrying out the reduction of metallic compound in the presence of the macromolecule dispersing agent that has sulfydryl in molecule.

13. the substrate of band light-blocking image as claimed in claim 12 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.

14. the substrate with light-blocking image, it is the substrate that comprises the band light-blocking image of the light-blocking image made from photosensitive transfer printing material, it is characterized in that,

Described photosensitive transfer printing material comprises supporter and the photonasty light shield layer that contains coloured composition that is provided with on described supporter,

Described coloured composition is by being 25.8MPa in the SP value ^1/2Contain the shape anisotropy metal particle in the following solvent and form, and

Described metal particle is by comprising that following operation is that the manufacture method of feature makes, the operation of described operation for carrying out the reduction of metallic compound in the presence of the macromolecule dispersing agent that has sulfydryl in molecule.

15. the substrate of band light-blocking image as claimed in claim 14 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.

16. a colour filter, it is the colour filter that contains coloured composition, it is characterized in that,

Described coloured composition is by being 25.8MPa in the SP value ^1/2Contain the shape anisotropy metal particle in the following solvent and form, and

Described metal particle is by comprising that following operation is that the manufacture method of feature makes, the operation of described operation for carrying out the reduction of metallic compound in the presence of the macromolecule dispersing agent that has sulfydryl in molecule.

17. colour filter as claimed in claim 16 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.

18. a liquid crystal indicator, it is the liquid crystal indicator that contains coloured composition, it is characterized in that,

Described coloured composition is by being 25.8MPa in the SP value ^1/2Contain the shape anisotropy metal particle in the following solvent and form, and

Described metal particle is by comprising that following operation is that the manufacture method of feature makes, the operation of described operation for carrying out the reduction of metallic compound in the presence of the macromolecule dispersing agent that has sulfydryl in molecule.

19. liquid crystal indicator as claimed in claim 18 is characterized in that,

Described shape anisotropy metal particle is connected by a plurality of metal particles and forms, and has different tones according to the variation of the connection length of described a plurality of metal particles.